W Ts 8 U1 P2

Photochemistry
Volume 36
A Specialist Periodical Report
Photochemistry
Volume 36
A Review of the Literature Published between

July 2003 and June 2004
Editor
I. Dunkin, University of Strathclyde, Glasgow, UK
Authors
N.S. Allen, Manchester Metropolitan University, UK
N.W.A. Geraghty, National University of Ireland, Galway, Ireland
A. Gilbert, University of Reading, UK
W.M. Horspool, Dundee, UK
If you buy this title on standing order, you will be given FREE access to
the chapters online. Please contact sales@rsc.org with proof of purchase to
arrange access to be set up.
Thank you.
ISBN-13: 978-0-85404-450-4
ISSN 0556-3860
A catalogue record for this book is available from the British Library
r The Royal Society of Chemistry 2007
All rights reserved
Apart from any fair dealing for the purpose of research or private study for
non-commercial purposes, or criticism or review as permitted under the terms of the UK
Copyright, Designs and Patents Act, 1988 and the Copyright and Related Rights
Regulations 2003, this publication may not be reproduced, stored or transmitted, in any
form or by any means, without the prior permission in writing of The Royal Society of
Chemistry, or in the case of reprographic reproduction only in accordance with the terms
of the licences issued by the Copyright Licensing Agency in the UK, or in accordance with
the terms of the licences issued by the appropriate Reproduction Rights Organization
outside the UK. Enquiries concerning reproduction outside the terms stated here should
be sent to The Royal Society of Chemistry at the address printed on this page.
Published by The Royal Society of Chemistry,

Thomas Graham House, Science Park, Milton Road,
Cambridge CB4 0WF, UK
Registered Charity Number 207890
For further information see our web site at www.rsc.org
Typeset by Macmillan India Ltd, Bangalore, India

Printed by Henry Lings, Dorchester, Dorset, UK
Contents
Cover
An energy level diagram overlaid
on the sun. Background image
reproduced by permission of
NASA.
Introduction and Review of the Year 1

By Ian R. Dunkin
Photolysis of Carbonyl Compounds 9

By William M. Horspool
1 Norrish Type I Reactions 10

2 Norrish Type II Reactions 11
2.1 1,5-Hydrogen Transfer 11
2.2 Other Hydrogen Transfers 15
3 Oxetane Formation 15
4 Miscellaneous Processes 17
4.1 Decarboxylation and Decarbonylation 17
4.2 Reactions of Miscellaneous Haloketones
and Acid Chlorides 18
4.3 Other Processes 19
References 20
v
vi Contents
Enone Cycloadditions and Rearrangements:

Photoreactions of Dienones and Quinones 23
1 Cycloaddition Reactions 23
1.1 Intermolecular Cycloadditions 23
1.2 Intramolecular Cycloadditions 29
2 Rearrangement Reactions 31
2.1 a, b-Unsaturad Systems 31
2.2 b, g-Unsaturated Systems 34
3 Photoreactions of Thymines and Related Compounds 35
3.1 Photoreactions of Pyridones 35
3.2 Photoreactions of Thymines, etc 36
4 Photochemistry of Dienones 39
4.1 Cross-conjugated Dienones 39
4.2 Linearly Conjugated Dienones 41
5 1,2-, 1,3- and 1,4-Diketones 42
5.1 Reactions of 1,2-Diketones and other
1,2-Dicarbonyl Compounds 42
5.2 Reactions of 1,3-Diketones 43
5.3 Reactions of 1,4-Diketones 44
5.4 Fulgides and Fulgimides 46
6 Quinones 48
6.1 p-Quinones 48
References 49
Photochemistry of Alkenes, Alkynes and Related Compounds 55

1 Reactions of Alkenes 55
1.1 cis,trans-Isomerization 55
1.2 Miscellaneous Reactions 65
2 Reactions involving Cyclopropane Rings 70
2.1 The Di-p-methane Rearrangement and Related Processes 70
2.2 Miscellaneous Reactions Involving three-membered
Ring Compounds 72
3 Reactions of Dienes and Trienes 74
4 (2p + 2p)-Intramolecular Additions 77
5 Dimerization and Intermolecular Additions 79
6 Miscellaneous Reactions 82
6.1 Reactions of Halo Compounds 82
Contents vii
6.2
Miscellaneous Rearrangements and Bond
Fission Processes 84
References 84
Photochemistry of Aromatic Compounds 91

By Andrew Gilbert
1 Introduction 91
2 Isomerization Reactions 91
3 Addition Reactions 94
4 Substitution Reactions 98
5 Cyclization Reactions 101
6 Dimerization Processes 119
7 Lateral Nuclear Shifts 121
8 Miscellaneous Photochemistry of Aromatic Systems 124
References 128
Photooxidation and Photoreduction 133

By Niall W. A. Geraghty
1 Introduction 133
2 Reduction of the Carbonyl Group 134
3 Reduction of Nitrogen-containing Compounds 136
4 Miscellaneous Reductions 142
5 Singlet Oxygen 146
5.1 Singlet Oxygen 146
5.2 Oxidation of Aliphatic Compounds 149
5.3 Oxidation of Aromatic Compounds 153
6 Other Oxidation Methods 155
6.1 Oxidation of Aliphatic Compounds 155
6.2 Oxidation of Aromatic Compounds 163
7 Oxidation of Nitrogen-containing Systems 175
8 Miscellaneous Oxidations 190
References 196
Photoelimination 205
By Ian R. Dunkin
1 Introduction 205
2 Elimination of Nitrogen from Azo Compounds and Analogues 205
viii Contents
3 Elimination of Nitrogen from Diazo

Compounds and Diazirines 207
3.1 Generation of Alkyl and Aryl Carbenes 207
3.2 Photolysis of a-Diazo Carbonyl and
Related Compounds 210
4 Elimination of Nitrogen from Azides and
5 Photoelimination of Carbon Monoxide and Carbon Dioxide 215
5.1 Photoelimination of CO from Organometallic
Compounds 217
6 Photoelimination of NO and NO2 218
7 Miscellaneous Photoeliminations and Photofragmentations 219
7.1 Photoelimination from Hydrocarbons 219
7.2 Photoeliminations from Organohalogen Compounds 220
7.3 Photofragmentations of Organosilicon Compounds 223
7.4 Photofragmentations of Organosulfur Compounds 224
7.5 Photolysis of o-Nitrobenzyl Derivatives and
7.6 Other Photofragmentations 227
References 228
Polymer Photochemistry 232

By Norman S. Allen
1 Introduction 232
2 Photopolymerization 232
2.1 Photoinitiated Addition Polymerization 233
2.2 Photocrosslinking 236
2.3 Photografting 243
3 Luminescence and Optical Properties 243
4 Photodegradation and Photooxidation
Processes in Polymers 262
4.1 Polyolefins 263
4.2 Polystyrenes 263
4.3 Poly(Acrylates) and -(Alkyl Acrylates) 263
4.4 Poly(Vinyl Halides) 264
4.5 Polyamides and Polyimides 264
4.6 Poly(Aromatics) 264
4.7 Silicone Polymers 264
4.8 Polyurethanes and Rubbers 264
4.9 Polyesters 264
4.10 Photoablation of Polymers 265
Contents ix
4.11 Natural Polymers 265

4.12 Miscellaneous Polymers 266
5 Photostabilization of Polymers 266
6 Photochemistry of Dyed and Pigmented Polymers 267
References 268
Introduction and Review of the Year
BY IAN R. DUNKIN
Department of Pure and Applied Chemistry, University of Strathclyde, Thomas
Graham Building, 295 Cathedral Street, G1 1XL, Glasgow, UK
This is a very special volume of Photochemistry, because it is to be the last in

the current format. It has been apparent in recent years that we are experienc-
ing a profound change in the way in which information of all types is
disseminated. In particular, more-or-less universally available on-line searching
for scientific papers and data has greatly speeded up the task of searching
the literature for material relevant to any area of interest. So much so, that the
inevitable time delay inherent in the production of review serials, such as the
Specialist Periodical Reports, now seems excessive. Moreover, the nature of
some other RSC publications has changed in the past few years. Chemical
Society Reviews, for example, has moved from being a vehicle for the compre-
hensive or historical coverage of selected topics to being more of a collection of
updates on the research of individual groups. This has left a niche in the review
coverage of the RSC, and the intention is to fill this with a new style of
Specialist Periodical Reports. In the future, from Volume 37 onwards, Photo-
chemistry will aim at providing a critical analysis of recently published research
in photochemistry, with less of an attempt at comprehensiveness. It also is
intended to emphasize applications of photochemistry in, for example, synthe-
sis, fabrication of new devices and materials, medicine, pollution control, etc.
At the same time, we must bid farewell to three reporters who have contrib-
uted indefatigably to the publication over many years. First of all, William
Horspool, who has written the first three chapters on organic photochemistry –
covering carbonyl compounds, enones and alkenes – for many volumes. The
sum of William’s contributions represents an enormously valuable and contin-
uous review of these topics, which will, I am sure, continue to be of benefit for
many years to come. Secondly, Norman Allen has carried out the Gargantuan
task of reviewing the field of polymer photochemistry, also for many years. His
contribution to the present volume, containing 949 references, is no exception
and well illustrates the size of this job. I am pleased to acknowledge the
sustained and enthusiastic contributions made by both William and Norman,
and thank them for their support during the brief time I have assumed this
responsibility of editorship.
Photochemistry, Volume 36
r The Royal Society of Chemistry, 2007
1
2 Photochemistry, 36, 2007, 1–8
Deserving special recognition for his contribution is Andrew Gilbert,

the third of our current contributors who is leaving at this time. Not only
has he written the chapters on aromatic photochemistry and photo-oxidation
and reduction for a good many years, but was also the Senior Reporter until I
took over for Volume 34. He has now passed over the photo-oxidation and
reduction chapter into the capable hands of Neil Geraghty, but continues
with his contribution on aromatic photochemistry in the current volume. Most
of all, though, Andrew merits our gratitude for maintaining both the quality
and breadth of coverage of Photochemistry in his long-held position of
Senior Reporter. As I am beginning to discover, finding the right authors,
with the necessary expertise and the willingness to commit to writing a
review annually for a considerable period, is no mean task, one which Andrew
has always managed with characteristic tact and persistence. I speak there-
fore not only for myself but also on behalf of the RSC in thanking him for
all the years of dedication which he has brought to the direction of
Photochemistry.
Having, with great pleasure, made these preliminary acknowledgements,
I move to my selection of photochemical highlights of the period reviewed in
this volume, which is as subjective and personal as ever. I continue to believe
that photochemistry needs to ‘earn its living’ in the chemical world and not be
just a subject of interest for a relatively closed group of specialists, a point
of view which will inform the new format Photochemistry in future volumes.
I have therefore looked especially to highlight work in which photochemistry
has accomplished something of real utility: efficient syntheses, the manufacture
of commercially useful devices, and biological, medical or environmental
applications, for example. As usual, the chapter and reference numbers of
the publications cited in this review can be found by using the Author Index,
but I have also included the chapter numbers to aid those who wish to scan for
chemical structures.
A good example of a high-yielding photoreaction of synthetic utility is
provided by the photoenol of the benzaldehyde (1), which can be trapped in
very good yield (81%) by methyl 2-ethylacrylate, acting as a dienophile, to give
the tetrahydronaphthalene derivative (2) (Nicolaou and Gray, Chapter 1).
Related, intramolecular reactions of photoenols have provided routes to poly-
cyclic carbon frameworks, such as the conversion of (3) into (4) (Nicolau et al.,
Chapter 1).
OMe OMe OH
Me CHO Me
OMe
MeO Me MeO O
OMe OMe
(1) (2)
Photochemistry, 36, 2007, 1–8 3
O OH
X X
H
H
(3) X = CO2Et, COMe, CN (4)
Scheffer et al. (Chapter 1) have shown how the use of ionic chiral auxiliaries
as a means of immobilizing ketoacids (5) within crystals results in excellent
yields of cyclized products upon irradiation, and with high ee. With (S)-(þ)-
1-phenylethylamine as the salt-forming amine, for example, a quantitative yield
of (6) with 98% ee was obtained. The corresponding R amine similarly gave a
quantitative yield of the enantiomer of (6) with an ee of 97%, and other chiral
amines were also tried with success.
R
R
O OH
(5) R = CO2 H3NR* (6)
The photocycloaddition of aldehydes to the 5-methoxyxoxazole (7) has been

developed by Griesbeck et al. (Chapter 1) as a path to esters of erythro-a-amino-
b-hydroxycarboxylic acids. The photoaddition, giving the intermediate bicyclic
oxetanes (8: R ¼ Ph, 2–naphthyl, BnCH2, Et, i–Pr, i–Bu), occurs with excellent
exo-diastereoselectivity (dr 4 98:2) and chemical yields are 485%. An intra-
molecular 2 þ 2 photocycloaddition has been exploited as the key step in the
synthesis of pentacyclic terpene systems, such as the formation of (10) from (9)
(de la Torre et al., Chapter 2). The yield of 63% for this example seems
reasonable in view of the complexity of the system. Nishimura and co-workers
(Chapter 3) have described the synthesis of a series of interesting crownopadd-
lanes by intramolecular photocycloadditions of the compounds (11: n ¼ 2–4),
while new crownophanes (12: n ¼ 2–4) were prepared by irradiation of the
corresponding divinyl derivatives. Pyridine analogues of (12) were also prepared.
O H
H
N H R N R
O
Me OMe Me
O O
OMe
(7) (8)
O O
H H
(9) (10)
HO2C CO2H
O O O O
O O
n n
(11) (12)
The irradiation of CBr4 in MeOH has been reported as an efficient photo-

chemical means of removing protecting groups (Chen et al., Chapter 3).
Examples are the release of (13b) from (13a) in 89% yield, and (14b) from
(14a) in 86% yield.
RO
RO OAc OR
O
AcO O
O AcO
O AcO
OMe
(13) a: R-R = CMe2 (14) a: R = Tf

b: R = H b: R = H
Potentially useful synthetic reactions may not always proceed in high yields.
The intramolecular meta photocycloadditions of (15: X ¼ CH2, SiMe2; R1, R2,
R3 ¼ H, Me), for example, gave the corresponding 1,6-bridged di-
hydrosemibullvalene adducts (16) in yields of only 7–19%, but starting with
relatively simple precursors provide an approach to complex molecular systems
not readily accessible by conventional means (Penkett et al., Chapter 4).
R1
O O X
X
O
O
3
R
R1 R2
R3
R2
(15) (16)
Photocyclizations of mono- and distyryl substituted polynuclear arenes in

the synthesis of helicenes have been reported by El Abed et al. (Chapter 4). In
this work, irradiation of toluene solutions of (17: R ¼ H, OMe, CN, Me, OH)
and (18: R1, R2 ¼ H, OMe, Me) with iodine in the presence of propylene oxide
as an HI scavenger, afforded 62–96% and 70–90% of the [5]- and [7]car-
bohelicenes (19) and (20), respectively, depending on the substituents. A
remarkable enhancement has been observed for the photocyclizations of 1-
allyloxy- and 1-allylamino-2-halogenoarenes, giving dihydrofurans and indoles
respectively, when an enolate ion is added as an entrainment reagent (Vaillard
et al., Chapter 4). The dihydrofuran (22), for example, was obtained in 55%
yield from irradiation of (21) but this was increased to 91% when the
CH3COCH2 ion was present; and similarly under the latter conditions the
yield of (24) from (23) was greater than 96%.
R R1
Br
(17)
R2
(18)
R1
Br
R
R2
(19) (20)
Me
Br
hν
O O
(21) (22)
Me
Br
hν
N N
(23) (24)
A microreactor has been described, based on SiO2 capillaries with the inner
walls covered with TiO2-coated colloidal SiO2 particles (Li et al., Chapter 5).
The reduction of methylene blue was carried out by injecting a solution of the
reactant through the microcapillary using a syringe pump, while irradiating at
254 nm, and a 150-fold increase in the reduction rate was obtained relative to a
comparable batch system.
The potential of using ceramic-based nanoparticles as carriers of photo-
sensitizers for photodynamic therapy (PDT) has been described (Roy et al.,
Chapter 5). As an example, the anticancer drug 2-devinyl-2-(1-hexyloxyethyl)
pyropheophorbide (25) has been encapsulated in the non-polar core of micelles
by hydrolysis of triethoxyvinylsilane. The resulting particles were uniform in size,
having an average diameter of 30 nm, and were stable in an aqueous medium.
The uptake of the nanoparticles by tumour cells, and significant cell death
following 1O2 generating irradiation at 650 nm, was then demonstrated in vitro.
The photooxygenation of trans-8-(acetyloxy)bicyclo[4.2.0]octa-2,4-dien-7-yl
acetate (26) was a key step in the stereospecific synthesis of a new inositol
analogue (27) (Kara and Balci, Chapter 5).
O(CH2)5CH3
Me
Me
Me
Me
NH N
N HN Me
Me
CO2H
(25)
OH
H OAc H OAc H OH
1O
HO
2, CCl4
O
O
OAc OAc HO OH
H H H
HO
(26) (27)
The trifluoromethyl group has long been considered as having a low

tendency to migrate to a carbene centre, and this seemed to explain why, for
example, photolysis of the diazoester (28) results in hydrogen abstraction
to give (29), rather than rearrangement. An investigation of the photolysis
of a 13C-labelled isotopomer of (28), however, has now shown that an estima-
ted 93.5% of the rearranged product (30) was produced by trifluoromethyl
migration (Haiss and Zeller, Chapter 6). Meldrum’s acid (31) undergoes
isomerization to the corresponding diazirine when irradiated at 355 nm, but
loss of N2 and Wolff rearrangement at 254 nm; the two processes clearly
occur from two different electronic excited states (Bogdanova and Popik,
Chapter 6).
O
O O H
H *
F3C O C
F3C OEt CF3
N2
(28) (29) (30)
O
O
N2
O
O
(31)
A very good example of the enormous benefits that DFT computations of

IR spectra have brought to matrix-isolation studies – giving the technique
a veritable new lease of life in the study of organic reactive intermediates – has
been provided by a study of the photolysis of a-pyrone (32) and its 4,6-dimethyl
derivative (Breda et al., Chapter 6). The photochemistry of a-pyrone was
the subject of some of the earliest matrix-isolation studies of organic species,
but the use of DFT computations has now allowed a virtually complete
identification of the individual rotamers of the ring opened aldehyde-ketene
(33)–(36).
C O O C O
O
O
(33) (34)
O
C O C O
(32)
O
O
(35) (36)
Wavelength dependent differential release of compounds from a solid-phase

resin has been demonstrated, using beads bifurcated with nitroveratryl (37) and
pivaloyl glycol (38) photo-linkers (Ladlow et al., Chapter 6). A narrow band-
width tuneable pulsed laser was used for photolysis, and it was found that the
nitroveratryl linker undergoes cleavage over a wide range of wavelengths, with
maximum cleavage rates at 320 and 340 nm, while the pivaloyl glycol linker is
photo-stable at wavelengths above 340 nm.
O
O
OTMS
O NO2
HO O
OH O OTBDMS
MeO HO
(37) (38)
Finally, it must be remarked that, as is so often the case, the real highlight in
polymer photochemistry (Chapter 7) for the review period is the sheer volume
of work in this field. Polymer photochemistry continues to be an active area of
applied photochemistry, with many topics growing in commercial and indus-
trial importance. New materials are constantly emerging from studies of
photopolymerization, photocuring and photocrosslinking, e.g. polymers with
useful mechanical and electronic properties and liquid crystalline materials.
Last year, for example, saw a virtual literature explosion in LEDs (light
emitting diodes), and in this year’s review it still represents one of the largest
specialized topics in photochemistry and photophysics.
Photolysis of Carbonyl Compounds
BY WILLIAM M. HORSPOOL
Dundee, UK
There is little doubt that photochemically induced single electron-transfer

(SET) processes are becoming of greater importance as the years pass and our
understanding of them increases. As a consequence, the area has attracted
exponents to compile reviews such as those by Hasegawa,1 who has reviewed
the application of photochemically induced SET reactions to organic mole-
cules, and Mattay and co-workers,2 who have reviewed the subject from
preparative and mechanistic standpoints. Another area that attracts much
attention is that of photochemical reactions within constrained media, and
reviews of this directed at reactions within zeolites have been published.3,4 The
behaviour of benzyl radials formed by the photochemical decomposition of
dibenzylketone in NaY zeolites has been monitored using 4-(3-hydroxy-
2-methyl-4-quinolinoyloxy)-2,2,6,6-tetramethylpiperidine-1-oxyl free radical
as a probe.5 Cyclodextrins also provide a useful constraining medium for
reactions, and b-cyclodextrin has been used in a study of the photochemical
behaviour of variously substituted ketones (1) attached to peptide links. The
results show that carbon-carbon bond formation is the outcome.6
The use of the XeCl excimer 308 nm radiation system has been described in
its application to scalable photochemical reactions of ketones.7
9
1 Norrish Type I Reactions
a-Fission processes are commonly brought about by the irradiation of alde-

hydes and ketones. The simplest example of these, formaldehyde, is no
exception, and studies have shown that the rate of photodissociation of
formaldehyde in a xenon matrix is greater than that in other matrices at a
variety of wavelengths.8 a-Fission into methyl and formyl radicals results on
irradiation of acetaldehyde at 308 nm in the gas-phase.9 Calculations have been
used to analyse the photofragmentation of crotonaldehyde.10
The Rydberg state of acetone was studied by irradiation at 195 nm.11 An
evaluation of the photodissociation of acetone at a series of wavelengths has
been published.12 Wu and co-workers13 have reported the results of calculation
on the low-lying pathways for the photodissociation of hydroxyacetone. The
reactions encountered are Norrish Type I processes and involve the fission of
either of the a-bonds. Albini and his co-workers14 have studied the Norrish
Type I activity of the hydroxyalkyl ketone moiety of triamcinolone (2).
As mentioned earlier in this chapter, irradiations within zeolites continue to

be of interest, and one study has shown that the irradiation of 1-naphthylacyl-
ates in NaY zeolites results in the formation of a single product. The selectivity
in this reaction is in contrast to the reaction of the same ketones in solution
when many products are formed. The authors suggest that the selectivity is due
to restriction around the biradical formed initially.15 A review article has
highlighted the control that can be exercised with cations on the photochem-
istry of ketones and other substrates contained within zeolites.16
The Norrish Type I reaction usually leads to decarbonylation. This is the
case with dicyclopropyl ketone on irradiation at 193 nm. Decarbonylation,
however, is a second step and this is preceded by ring opening of the
cyclopropyl moieties to diallyl ketone.17 Calculations have shown that dec-
arbonylation of cyclobutanone occurs from the np* triplet state. The resultant
triplet trimethylene biradical undergoes ISC to the ground state before forma-
tion of cyclopropane. On the other hand, the cycloelimination reaction to yield
ketene and ethene arises from the singlet excited state.18 Irradiation of
cyclopentanone in aqueous and frozen aqueous solutions has been examined
and the influence of applied magnetic fields assessed.19 Photodecarbonylation
in the crystalline phase of the ketone (3) at 310 nm takes place stereospecifically
with the formation of the cyclopentane derivative (4). The latter can be readily
transformed into racemic herbertenolide (5).20
Irradiation of the ketone (6) in argon-degassed cyclohexane brings about

Norrish Type I fission. In this case decarbonylation does not result and the
triplet biradical formed by the fission affords the aldehyde (7). The enol (8) is
also a product of this irradiation.21 An aldehyde is also the principal product on
irradiation of (9) in benzene. The a-fission affords the aldehyde derivative (10)
in 90% yield.22 Analogous behaviour is observed on irradiation of bicyclo-
heptanone (11) to afford an aldehyde that was a key intermediate in the
synthesis of dimethyl secologanoside.23
2 Norrish Type II Reactions

2.1 1,5-Hydrogen Transfer. – Both experimental and theoretical approaches
have been used to study the reactivity of n-butyrophenone included in alkali-
metal-exchanged zeolites. The results indicate that with smaller cations the
Norrish Type I process is enhanced over the Norrish Type II reaction.24 Others
have reported that the photochemical decomposition of n-butyrophenone in a
variety of solvents follows first-order kinetics.25
a-Chlorovalerophenone undergoes a normal Norrish Type II cyclization
path on irradiation. Interestingly, the corresponding a-bromovalerophenone
undergoes only C–Br fission on irradiation.26 The ketone (12) undergoes
Norrish Type II hydrogen abstraction to afford the usual biradicals, which can
cyclize into cyclobutanols. Both the cis-(13) and the trans-isomeric forms are
possible. This particular investigation has studied the influence of antibodies
(12B4, 20F10 ad 21H9) on the cyclization reaction. The authors observed that
the most reactive antibody, 20F10, catalyses the formation of the cis-product
(13).27
The benzaldehyde derivative (14) undergoes Norrish Type II hydrogen

abstraction with the formation of a photoenol. This enol can be trapped
efficiently (81% yield) using methyl 2-ethylacrylate as the dienophile, to afford
the tetrahydronaphthalene derivative (15).28 A detailed analysis of intramole-
cular versions of the addition to photoenols has been described. The method
provides a path to polycyclic carbon frameworks such as the conversion of (16)
into (17). Examples are also reported using a four-carbon chain separating the
dienophile from the photoenol.29 Bach and co-workers30 have demonstrated
that irradiation of the aldehyde (18) affords the corresponding o-quinodi-
methane derivative by a Norrish Type II process. 1,4-Biradicals are formed
on irradiation of [4-(11-mercaptoundecyl)phenyl](2-methylphenyl)methanone
as a monolayer. The biradicals collapse to yield photoenol intermediates that
can be trapped in a Diels-Alder reaction.31 A study of the photochemical
behaviour of the pyridyl aldehydes (19) has reported that irradiation brings
about colour changes. Only the derivative (19e) undergoes Norrish Type II
hydrogen abstraction with formation of the corresponding cyclobutene
derivative.32
The Norrish Type II reactivity of the acetophenone derivatives (20) has been
exploited as a new photoremovable protecting system for carboxylic acids. The
irradiation affords the usual 1,5-biradicals that then release the acids (21) in
the yields shown in parenthesis. Irradiation times are short.33 Klan and co-
workers34 have described the photochemical reactivity of 1,5-dimethylphenacyl
phosphoric and sulfonic esters.
Chong and Scheffer35 have examined the photochemical and thermal reac-
tions of the ketonic carboxylates (22). The photoreactions of the carboxylate
salts are carried out in the crystalline phase, and the hydrogen abstraction
reaction and ring opening of the cyclopropyl ring results in the formation of
(23) with almost quantitative ee. The thermal reactions also afford the same
product but with much lower ee. Scheffer et al.36 have also described the use of
ionic chiral auxiliaries as a means of immobilizing ketoacids (24) within
crystals. The irradiation of these gives excellent yields of either of the cyclized
products (25) and (26). Thus, using (S)-(þ)-1-phenylethylamine as the amine
salt affords a quantitative yield of (25) with 98% ee. The corresponding (R)-
amine again gives a quantitative yield of product but this time the products is
(26) with an ee of 97%. The same enantiomer (26) is obtained using (1S,2R)-
(–)-1-amino-2-indanol with an ee of 96%, while (1S,2S)-(þ)-2-amino-3-
methoxy-1-phenyl-1-propanol affords (25) with an ee of 95%.
Norrish Type II hydrogen abstraction is the predominant reaction on irradia-

tion of the silylated ketones (27). This affords the dealkylated product (28). There
is some Norrish Type I reactivity that results in the formation of the isomerized
product (29) and the two ring-opened products (30) and (31). The ratio of the
two reactions varies with the silyl group, with a 32:1 ratio of (28):(29) obtained
from (27, R ¼ Me) and a 13:1 ratio from (27, R ¼ Ph or R3 ¼ MePh2).37
2.2 Other Hydrogen Transfers. – A full account of the photochemical reaction

of ketones with leaving groups adjacent to the carbonyl function has been
published.38 This study provides a route to a variety of di- and tri-substituted
cyclopropyl ketones. Calculations have been carried out on the photobehaviour
of a-substituted butyrophenones to establish a mechanism whereby cyclopro-
pane systems can be formed.39 The photochemical behaviour inducing a
hydrogen transfer reaction of 2-(o-tolyl)benzofuran-3-one has been studied.40
3 Oxetane Formation
Griesbeck41 has published an account of how stereoselectivity in single and

triplet addition reactions to afford oxetanes is linked to spin selectivity. A study
of the stereo- and regioselectivity of oxetane formation by addition of alde-
hydes to substituted furans (Scheme 1) has been carried out. The total yield of
adducts is high at 95%. The reactions are regio-random but stereoselective,
affording an exo:endo ratio of 97:3 for the addition of benzaldehyde. The
authors42 argue that the 1,4-biradicals formed in the addition reaction are the
key to explaining the photochemical addition. D’Auria et al.43 have shown that
the addition of benzaldehyde to furan affords the exo-adduct selectively. This
selectivity is explained on the basis of adduct stability.
The cycloaddition of aldehydes to the 5-methoxyxoxazole derivatives shown in
Scheme 2 has been developed as a path to esters of erythro-a-amino-b-hydroxy-
carboxylic acids. The photoaddition occurs with excellent exo-diastereoselec-
tivity. The dr obtained is 498:2 and chemical yields are 485%.44
Intramolecular oxetane formation has been examined in the sclareolide
system. Typical examples are the photocyclizations of the substituted keto
derivatives (32) and (33). The yields obtained are high in this series.45
Scheme 1
Scheme 2
The sensitizer dependency for the cycloreversion of trans,trans-2,3-diphenyl-

4-methyloxetane has been studied. When chloranil is used as the sensitizer, the
reaction proceeds via the radical cation of trans-b-methylstyrene, while with
pyrylium salts the trans-stilbene radical cation is involved.46 Other work in this
area has examined the cycloreversion of the oxetanes (34) using (35) or
chloranil as the sensitizers.47
4 Miscellaneous Processes
A mixture of carbohydrates is formed on irradiation of formaldehyde at 77 K.

The authors48 suggest that hydroxymethylene formation is the key to this and
that addition of this intermediate to formaldehyde yields glyoxaldehyde.
The photodecomposition of 4-(6-methoxy-2-naphthyl)butan-2-one (nabume-
tone) in water probably involves the formation of the nabumetone radical
cation. This leads to the formation of 6-methoxy-2-naphthalene carboxalde-
hyde.49 Further study has examined the photodegradation of this ketone in
n-butanol where it was shown that a first-order degradation took place. An
excited singlet state is involved, and the author50 proposes that both concen-
tration and hydrogen bonding are important in this solvent.
Irradiation of 4-methyl-5-p-anisyl substituted N-alkoxythiazolethiones
brings about N–O bond homolysis with the formation of alkoxy radicals. This
technique has been applied to the synthesis the compound (36).51 The aldehyde
(37) undergoes addition to dimesitylsilene when it is irradiated at –571C in
hexane. The product, obtained in 76% yield, was identified as (38).
4.1 Decarboxylation and Decarbonylation. – The potential energy surfaces for

the dissociation of formic acid have been determined by ab initio methods.52
The photochemical dissociation of simple amides such as formamide, aceta-
mide and N-methylacetamide has been investigated using CASSCF/MRSDCI
single point calculations.53
Mori et al.54 have studied the decarboxylation of (39) under a variety of
conditions and have found that the conversion to (40) occurs without the
involvement of radicals. They suggest that the process is a concerted cheletropic
extrusion via the s-cis conformation. A further study55 has examined the
photodecarboxylation of the (S)-ester (39) in unstretched-polyethylene films.
The decarboxylation affords (40) with complete retention of the stereochem-
istry. The yield of product is 98% and the ee is 498%. The photochemical
behaviour of the ester in other confining media such as cyclodextrins indicates
that cage-escape products are also formed. The irradiation of grandifloric acid
(41) at 254 nm in acetonitrile brings about decarboxylation with the formation
of epimers. In methanol a different reaction occurs that results in the conver-
sion of the C-methyl group into a carbomethoxy substituent.56
The photoreactivity of indoprofen is centred on the propionic acid moiety

within the molecule.57 The salt of ketoprofen (42) is known to undergo
decarboxylation to afford the anion (43). The present study has demonstrated
that, under carefully controlled conditions in THF, the lifetime of the carba-
nion can be extended to many hours.58 Roberts and Pincock59 report that a
carbocation is formed on irradiation of the acetate (44) in 2,2,2-trifluoroethanol
and methanol.
Pyruvic acid undergoes elimination of an OH radical on irradiation at 193

nm, a process involving the T1 excited state.60 Calculations have shown that
photodissociation of formylcyanide is unlikely to occur from the excited singlet
state.61
4.2 Reactions of Miscellaneous Haloketones and Acid Chlorides. – UV irradia-

tion of fluorocarbonyl iodide results in the formation of (OCIF). . .I and
(OCFI). . .F complexes,62 while ab initio methods have been used to interpret
the photoreactivity of bromoacetyl chloride.63 A further study on the latter
system has shown that the C–Cl bond ruptures on irradiation at 248 nm.64
a-Iodoketones (45) undergo facile conversion to the corresponding a-

hydroxyketones (46) in the yields shown.65 Morrison and his co-workers66
have described evidence for the interaction between the ketone and the CBr
moieties in 17a-bromo-3a-(triphenylsiloxy)-5a-androstan-6-one.
4.3 Other Processes. – The quantum yield for the release of benzoic acid from
2,5-dimethylphenacyl benzoate is temperature dependent in benzene solution.
At room temperature f ¼ 0.22, while at 501C the value rises to 0.28. A much
greater effect is observed in methanol or ethanol, when there is a threefold
increase in the quantum yield. The authors67 suggest that the reaction in heated
methanol enhances the E-photoenol population. Givens and Lee68 have
reviewed the use of the p-hydroxyphenacyl moiety as a photoprotecting group
for biological substrates.
1- and 2-Naphthoyloxyl radicals can be formed by irradiation of the 2-
pyridone derivatives (47) and (48), respectively. Apparently the presence of a
methoxy group in the ring prevents decarboxylation.69
The SET-induced ring opening of the cyclopropyl moiety in (49) results in

its conversion to the mixture of products (40:3) shown in Scheme 3. The
best results are obtained using a mixture of MeCN/5 equivalents Et3N/1
equivalent LiClO4. These conditions were also applied to (50) that ring-opens
to yield (51).70
Scheme 3
References
1. (a) E. Hasegawa, Kokagaku, 2003, 33, 220; (b) E. Hasegawa, Chem. Abstr., 2003,
139, 36091.
2. P. Schmoldt, H. Rinderhagen and J. Mattay, Mol. Supramol. Chem., 2003, 9, 185.
3. J. Sivaguru, J. Shailaja and V. Ramamurthy, in: Handbook of Zeolite Science and
Technology, ed. S.M. Auerbach, K.A. Carrado and P.K. Dutta, Marcel Dekker,
New York, 2003, p. 515.
4. S. Hashimoto, J. Photochem. Photobiol. C: Photochem. Rev., 2003, 4, 19.
5. (a) A. Aspee, L. Maretti and J.C. Scaiano, Photochem. Photobiol. Sci., 2003, 2, 1125;
(b) A. Aspee, L. Maretti and J.C. Scaiano, Chem. Abstr., 2004, 140, 198945.
6. V. Jullian, F. Courtois, G. Bolbach and G. Chassaing, Tetrahedron Lett., 2003
44, 6437.
7. (a) A.G. Griesbeck, N. Maptue, S. Bondock and M. Oelgemoeller, Photochem.
Photobiol. Sci., 2003, 2, 450; (b) A.G. Griesbeck, N. Maptue, S. Bondock and M.
Oelgemoeller, Chem. Abstr., 2003, 139, 149181.
8. K.J. Vaskonen and H.M. Kunttu, J. Phys. Chem. A., 2003, 107, 5881.
9. M. Cordeiro, D.S. Natalia, E. Martinez-Nunez, A. Fernandez-Ramos and
S.A. Vazquez, Chem. Phys. Lett., 2003, 375, 591.
10. (a) M.-C. Wang, H.-l. Guo and B.-Z. Yan, Beijing Huagong Daxue Xuebao, Ziran
Kexueban, 2003, 30, 59; (b) M.-C. Wang, H.-l. Guo and B.-Z. Yan, Chem. Abstr.,
2004, 140, 286875.
11. W.-K. Chen, J.-W. Ho and P.-Y. Cheng, Chem. Phys. Lett., 2003, 380, 411.
12. E. Martinez-Nunez, A. Fernandez-Ramos, M.N.D.S. Cordeiro, S.A. Vazquez,
F.J. Aoiz and L. Banares, J. Chem. Phys., 2003, 119, 10618.
13. Y. Wu, D. Xie and Y. Yue, J. Comput. Chem., 2003, 24, 931.
14. G. Miolo, A. Ricci, S. Caffieri, L. Levorato, E. Fasani and A. Albini, Photochem.
Photobiol., 2003, 78, 425.
15. M. Warrier, L.S. Kaanumalle and V. Ramamurthy, Can. J. Chem., 2003, 81, 620.
16. V. Ramamurthy, J. Shailaja, L.S. Kaanumalle, R.B. Sunoj and J. Chandresekhar,
J. Chem. Soc., Chem. Commun., 2003, 1987.
17. S.M. Clegg, B.F. Parsons, S. J. Klippenstein and D.L. Osborn, J. Chem. Phys., 2003,
119, 7222.
18. Y. Chen and S. Ye, Int. J. Quantum Chem., 2004, 97, 725.
19. E.D. Skakovskii, M.M. Ogorodnikova, L. Yu. Tychinskaya, V.L. Murashko,
N.G. Kozlov and S.V. Rykov, J. Appl. Spectroscop., 2004, 71, 22.
20. D. Ng, Z. Yang and M.A. Garcia-Garibay, Org. Lett., 2004, 6, 645.
21. B. Sket, B. Kosmrlj, M. Harej and D. Dolenc, Tetrahedron Lett., 2003, 44, 4247.
22. M.Y. Chang, C.H. Lin and N.C. Chang, Tetrahedron, 2004, 60, 1581.
23. (a) H.-M. Tai, M.-H. Huang and C.-C. Yang, J. Chin. Chem. Soc. (Taipei, Taiwan),
2003, 50, 441; (b) H.-M. Tai, M.-H. Huang and C.-C. Yang, Chem. Abstr., 2003,
139, 307897.
24. H. Yamashita, S. Takada, M. Hada, H. Nakatsuji and M. Anpo, J. Photochem.
Photobiol. A: Chem., 2003, 160, 37.
25. J.-Y. Hu and E.W.-J. Zhang, Huanjing Huaxue, 2004, 23, 168.
26. S. Cho and B.S. Park, Bull. Korean Chem. Soc., 2004, 25, 42.
27. S. Saphier, S.C. Sinha and E. Keinan, Angew. Chem. Int. Edn., 2003, 42, 1378.
28. K.C. Nicolaou and D.L.F. Gray, J. Am. Chem. Soc., 2004, 126, 607.
29. K.C. Nicolaou, D.L.F. Gray and J. S Tae, J. Am. Chem. Soc., 2004, 126, 613.
30. B. Grosch, C.N. Orlebar, E. Herdtweck, M. Eberhardt, W. Massa and T. Bach,
Angew. Chem. Int. Edn., 2003, 42, 3693.
31. A.J. Kell, C.C. Montcalm and M.S. Workentin, Can. J. Chem., 2003, 81, 484.
32. P. Mal, U.P. Lourderaj, P. Venugopalan, J.N. Moorthy and N. Sathyamurthy,
J. Org. Chem., 2003, 68, 3446.
33. W.N. Atemnkeng, L.D. Louisiana, P.K. Yong, B. Vottero and A. Banerjee, Org.
Lett., 2003, 5, 4469.
34. (a) P. Klan, A.P. Pelliccioli, T. Pospisil and J. Wirz, Photochem. Photobiol. Sci.,
2002, 1, 920; (b) P. Klan, A.P. Pelliccioli, T. Pospisil and J. Wirz, Chem. Abstr.,
2003, 138, 287151.
35. K.C.W. Chong and J.R. Scheffer, J. Am. Chem. Soc., 2003, 125, 4040.
36. B.O. Patrick, J.R. Scheffer and C. Scott, Angew. Chem., Int. Ed., 2003, 42, 3775.
37. J.R. Hwu, B.-L. Chen, C.-F. Lin and B.L. Murr, J. Organomet. Chem., 2003, 686,
198.
38. P. Wessig and O. Muhling, Helv. Chim. Acta, 2003, 86, 865.
39. W.-H. Fang and D.L. Phillips, J. Theoret. Comput. Chem., 2003, 2, 23.
40. (a) E. Koh, B.S. Park, H. Yoon and W.K. Woo, J. Photosci., 2002, 9, 13; (b) E. Koh,
B.S. Park, H. Yoon and W.K. Woo, Chem. Abstr., 2003, 138, 385243.
41. A.G. Griesbeck, J. Photosci., 2003, 10, 49.
42. M. Abe, T. Kawakami, S. Ohata, K. Nozaki and M. Nojima, J. Am. Chem. Soc.,
2004, 126, 2838.
43. M. D’Auria, L. Emanuele and R. Racioppi, J. Photochem. Photobiol. A: Chem.,
2004, 163, 103.
44. A.G. Griesbeck, S. Bondock and J. Lex, J. Org. Chem., 2003, 68, 9899.
45. M.C. de la Torre, I. Garcia and M.A. Sierra, J. Org. Chem., 2003, 68, 6611.
46. M.A. Miranda and M. Angeles Izquierdo, Photochem. Photobiol. Sci., 2003, 2, 848.
47. M.A. Miranda and M.A. Izquierdo, Eur. J. Org. Chem., 2004, 1424.
48. M. Yamauchi and S.N. Ahmed, J. Undergrad. Chem. Res., 2003, 2, 29.
49. M. Valero and S.M.B. Costa, J. Photochem. Photobiol. A: Chem., 2003, 157, 93.
50. M. Valero, J. Photochem. Photobiol. A: Chem., 2004, 163, 159.
51. J. Hartung, T. Gottwald and K. Spehar, Synlett., 2003, 227.
52. H.Y. He and W.H. Fang, J. Am. Chem. Soc., 2003, 125, 16139.
53. X.B. Chen, W.H. Fang and D.C. Fang, J. Am. Chem. Soc., 2003, 125, 9689.
54. T. Mori, H. Saito and Y. Inoue, J. Chem. Soc., Chem. Commun., 2003, 2302.
55. T. Mori, Y. Inoue and R.G. Weiss, Org. Lett., 2003, 5, 4661.
56. S. Buscemi, S. Rosselli, M. Bruno, L. Scaglioni, N. Vivona and F. Piozzi,
J. Photochem. Photobiol. A: Chem., 2004, 163, 381.
57. V. Lhiaubet-Vallet, J. Trzcionka, S. Encinas, M.A. Miranda and N. Chouini-Lalanne,
Photochem. Photobiol., 2003, 77, 487.
58. M. Laferriere, C.N. Sanrame and J.C. Scaiano, Org. Lett., 2004, 6, 873.
59. J.C. Roberts and J.A. Pincock, Can. J. Chem., 2003, 81, 709.
60. S. Dhanya, D.K. Maity, H.P. Upadhyaya, A. Kumar, P.D. Naik and R.D. Saini,
J. Chem. Phys., 2003, 18, 10093.
61. (a) W.-J. Ding, W.-H. Fang and R.-Z. Liu, Chem. Phys. Lett., 2003, 369, 570;
(b) W.-J. Ding, W.-H. Fang and R.-Z. Liu, Chem. Abstr., 2003, 138, 368357.
62. M.S. Chiappero, G.A. Arguello, P. Garcia, H. Pernice, H. Willner, H. Oberhammer,
K.A. Peterson and J.S. Francisco, Chem.-Eur. J., 2004, 10, 917.
63. M.-C. Bacchus-Montabonel, N. Vaeck, B. Lasorne and M. Desouter-Lecomte,
Chem. Phys. Lett., 2003, 374, 307.
64. B. Lasorne, M.-C. Bacchus-Montabonel, N. Vaeck and M. Desouter-Lecomte,
J. Chem. Phys., 2004, 120, 1271.
65. C.A. Horiuchi, A. Takeda, W. Chai, K. Ohwada, S.J. Ji and T.T. Takahashi,
Tetrahedron Lett., 2003, 52, 9307.
66. W.S. Li, L. Torun and H. Morrison, Can. J. Chem., 2003, 81, 660.
67. J. Literik, S. Relich, P. Kulhanek and P. Klan, Molecular Diversity, 2003, 7, 265.
68. (a) R.S. Givens and J.-I. Lee, J. Photosci., 2003, 10, 37; (b) R.S. Givens and J.-I. Lee,
Chem. Abstr., 2004, 140, 217043.
69. T. Najiwara, J. Hashimoto, K. Segawa and H. Sakuragi, Bull. Chem. Soc. Jpn.,
2003, 76, 575.
70. N. Tzvetkov, M. Schmidtmann, A. Muller and J. Mattay, Tetrahedron Lett., 2003,
44, 5979.
Enone Cycloadditions and Rearrangements:
Photoreactions of Dienones and Quinones
Dundee, UK
1 Cycloaddition Reactions
Kakiuchi1 has reviewed some recent advances in enantioselective (2 þ 2)- and (2

þ 4)-photocycloaddition reactions in solution. Particular attention is given to
the use of chiral host molecules and chiral auxiliary groups.
1.1 Intermolecular Cycloadditions

1.1.1 Open-Chain Systems. The influence of hydrogen bonding on the out-
come of photochemical reactions between hydroxy derivatives of substituted
chalcones has been studied in the crystalline phase.2 The reaction in Scheme 1
has been examined to establish the difference between exciplex and CT
excitation. The results obtained from the two excitation paths are quite
different, with different yields and different de values. For example, direct
irradiation involving the exciplex in toluene at 501C yields the two products in
6% and 5% yields, respectively. The de values are 53 and þ1. Charge-transfer
excitation, however, at the same temperature affords yields of 4% and 10%
with de values of þ52 and 9.3
Scheme 1
The photochemical (2 þ 2)-dimerization between trans-cinnamates contained

within a photocrosslinkable dendrimer has been reported. The cycloaddition is
accompanied by trans-cis isomerism.4 The b-form of trans-2,4-dichlorocinnamic
acid dimerizes on irradiation to give the b-truxinic acid derivative in a first-order
kinetic process.5 Others6 have studied the influence of substituents on the aryl
ring of cinnamic acid, with a view to control crystal engineering. Ito et al.7 have
reported the photodimerization in the solid state of cinnamic acids (1) as their
23
ammonium salts. This treatment yields mainly the b-(2) and d-(3) truxinic dimers.
Imidazole salts are also reactive in this process. The control of the dimerization
of cinnamates has been demonstrated using 5,5-dihexylbarbituric acid as a
template. A marked efficiency of dimerization was observed.8
The photochemical addition of methyl 2,3-dioxopentanoate to terpinolene

provides (2 þ 2)-cycloadducts that can undergo retro-aldol ring opening to
afford cyclohexane derivatives.9 The enol of acetylacetone undergoes photo-
addition to the isocarbostyril (4) resulting in the formation of two (2 þ 2)-
cycloaddition products that undergo retro-aldol ring opening (Scheme 2). The
first of these ring-opened compounds can be cyclized to yield the enone (5). An
intramolecular version of this photocycloaddition has also been studied using
the derivative (6). Here again two adducts (7) and (8) are produced on
Scheme 2
irradiation, and the former (7) can also be cyclized to yield the galanthan ring
system shown as (9). The (2þ2)-photodimerization within crystals of 5-benzyl-
idene-2-(4-chlorobenzyl)cyclopentanone brings about changes within the crys-
tal structure as the dimerization progresses.10 (2þ2)-Cycloaddition takes place
on irradiation of the enone (10) providing (11), which has been used as a key
intermediate in a synthesis of pentacyclic terpene systems.11
Photocycloaddition of dimethyl cyclobut-1-ene dicarboxylate to cyclohexene

affords the two products shown in Scheme 3. The former of these adducts,
obtained in 44% yield, is thermally unstable and undergoes ring opening to
yield (4Z,10Z) dimethyl cyclodeca-4,10-diene-1,4-dicarboxylate.12
Scheme 3
1.1.2 Intermolecular Additions to Cyclopentenones and Related Systems.

Mehta and co-workers13 have described the photochemical addition of 1,2-
dichloroethene to the enone (12). This affords the adduct (13), which can be
transformed into the protoilludane-type molecule shown in Scheme 4. A further
study related to the (2 þ 2)-cycloaddition reactions of compounds such as (14)
and (15) has determined the crystal structures of these compounds. The
Scheme 4
structures obtained are claimed to be in good agreement with the diastereo-

facial selectivity observed for these compounds.14
1.1.3 Intermolecular Additions to Cyclohexenones and Related Systems. Cal-

culations have been reported that deal with a transition state analysis of the
regioselectivity encountered in triplet-state (2 þ 2)-cycloaddition reactions of
cyclohex-2-enone.15 Diastereoselective (2 þ 2)-cycloaddition of ethene to
cyclohexenone carboxylates in the presence of chiral auxiliaries has been
described. Yields of bicyclo[4.2.0]octanone derivatives can be obtained with
de as high as 81%.16 The enone (16) can be tethered to a polymer substrate via
the tether group R. Irradiation of this material in toluene with ethene at 781C
gives a 68% yield of the adduct (17). The de of the product is reasonable at
72%.17 Addition of 1,1-diethoxyethene to the cyclohexenone (18, R ¼ Ph)
results in the formation of the two stereoisomeric head-to-tail regioisomers (19)
and (20). The outcome of the reaction is dependent on the rate of formation of
1,4-biradical intermediates. This can be seen in the dependence of the cis/trans
ratio on the solvent and on the temperature at which the reaction is carried out.
Thus with enone (18, R ¼ Ph) in acetone at 31C, a c/t ratio of 4.4 is obtained,
and this changes to 2.1 at 401C. In acetonitrile the c/t ratio is only 1.9 at the
same temperature. With the other derivative of (18), the c/t ratio is 1.3 in
acetone and 0.8 in acetonitrile.18 Photoaddition of ethene to the enone
carboxylate [21, R* ¼ ()-8-(2-naphthyl)menthyl] results in the formation of
the diastereoisomers (22) and (23) with a de of 56% at 781C. The diastereo-
selectivity can be enhanced by the addition of naphthalene derivatives to the
solution. Thus with naphthalene, a de of 71% is obtained, and this can be
increased to 83% with 1-phenylnaphthalene.19
Margaretha and co-workers20 have described the cycloaddition of some

cyclohex-2-enones to acrylonitrile. The addition reactions show moderate
regioselectivity and form mixtures of exo- and endo-5-oxobicyclo[4.2.0]-
octane-7-carbonitriles. Madhavan and Pitchumani21 have reported the dimer-
ization of 2-cyclohexenone confined in clay interlayers (cation-exchanged
bentonite). The reaction is remarkably regioselective and affords the head-
to-head dimer almost exclusively. The cyclic alkene (24) undergoes photo-
chemical addition to enones to afford the adducts (25) and (26) in the yields
shown.22
A patent has been lodged dealing with the photochemical addition of styrene
to the substituted benzopyranone (27, W ¼ CO2Et, R1–R4 ¼ H), which results
in the formation of the adduct (28) in high yield. This is part of a larger study of
the cycloaddition of such compounds.23 Lehn and co-workers24 have described
the dimerization of some coumarins (29) as 2:1 complexes with receptor
molecules such as (30). The photochemical dimerization within these complexes
affords, for example, the dimer (31), selectively. The photodimerization of the
6-alkylcoumarins (32) has been examined in solvents and micelles. With the 6-
methyl derivative the anti head-to-head dimer (33) was formed exclusively on
triplet sensitization in non-polar solvents. The syn head-to-head dimers (34)
were formed in ionic micellar conditions. Coumarin derivatives with longer
alkyl groups at C-6 also lead to the photo-dimers.25 The triplet-state properties
of coumarin and a series of 6-alkyl derivatives have been studied.26 The
coumarin moieties attached to a pentacyclo[9.5.1.13,9.15,15.17,13]octasilane with
eight coumarin groups undergo intermolecular (2 þ 2)-additions, resulting in
the linking of the monomeric units.27 7-Chlorodimethylsilanoxy-4-methyl
coumarin undergoes (2 þ 2)-photocycloaddition on irradiation at 310 nm
within a copolymer containing styrene units.28 Flavone derivatives have been
shown to undergo conversion into 2,2 0 -biflavanones on irradiation in the
presence of triethylamine.29
1.2 Intramolecular Cycloadditions. – (2 þ 2)-Photocycloaddition within the

chalcones (35) results in the formation of cyclobutane derivatives. The process
can be brought about using sunlight irradiation of solutions in chloroform, but
better yields (ca. 85%) can be achieved using l ¼ 350 nm.30
1.2.1 Intramolecular Additions to Cyclopentenones and Related Systems. The

unsaturated lactones shown in Scheme 5 can undergo photocycloadditions
Scheme 5
under the conditions described, to afford the intramolecular adducts. The yields
of product are all reasonable.31 Acetone-sensitized irradiation of (36) affords
the adduct (37) in 70% yield. This product is suggested as a key synthetic
intermediate in a synthesis of the cyclobutanone core of solanoeclepin A.32
1.2.2 Intramolecular Additions to Cyclohexenones and Related Systems. 3–

Styrylcyclohex-2-enone undergoes photochemical cyclization to afford 2,3-
dihydro-[1H]-phenanthrene-4-one.33 Work carried out on the photostability
of curcumin has also examined the photolability of the chalcone (38). This
undergoes cyclization to (39) on irradiation.34
2 Rearrangement Reactions
2.1 a,b-Unsaturated Systems

2.1.1 Isomerization. Sunlight irradiation of E-octyl p-methoxycinnamate re-
sults in conversion to the Z-isomer.35 The photochemically induced conforma-
tional changes of enolic (trifluoroacetyl)acetone have been studied in detail.36
The ring-opening reactions of (40) and (41), in the presence of chloranil and
(42) as electron-transfer sensitizers, has been studied. Enone (40) reacts only
under chloranil sensitization and affords the two products (43) and (44) after 10
min irradiation in methylene chloride. Compound (41) affords (45) with
chloranil and (46) under sensitization with (42). It is clear from these studies
and from the types of products formed that radical cation intermediates are
involved.37,38
The photoisomerization of retinal has been studied using super-short light

pulses,39 and the neutral and protonated forms of the retinal analogue (47) have
been examined by time-resolved methods.40 The irradiation of b-ionone as a
complex with b-CD in water leads only to the formation of retro-g-ionone.41
Time-dependent functional theory has been used to study the gas-phase

isomerism of urocanic acid (48).42 The photoisomerism of b-nor-5,10-seco-
steroidal ketones has been studied.43
2.1.2 Hydrogen Abstraction Reactions. The photo-deconjugation of the di-

acetone D–glucose derivatives (49) results in reactions that generally provide
products (50) and (51) with high de.44
Quantum mechanical studies have been carried out on the hydroxychalcone

(52) in an investigation of the one-way isomerization of the system.45 Kaneda
and Arai46 have described the photochemical hydrogen-transfer reactivity of
the enone (53).
2.1.3 Addition and Cyclization Reactions. Benzocyclobutenone undergoes

ring opening on flash photolysis, to afford 6-methylene-2,4-cyclohexadienyl-
ketene.47 A report has given details of the highly selective sequential addition
and cyclization reactions illustrated in Scheme 6. The reactions in Scheme 6
show the results with t-butyl acrylate, but other acrylate derivatives are also
effective.48 Hoffmann and Goerner49 have studied the electron transfer from
Scheme 6
N-methylpyrrolidine to a number of ketones. When these intermediates are

generated in the presence of (5R)-5-menthyloxyfuran-2[5H]-one addition takes
place to the double bond of the furanone. The adducts obtained from the
addition of vinylene carbonate to such homochiral furanones have been used in
a new stereoselective synthesis of butyrolactones of lyxofuranose.50
2.1.4 Miscellaneous Reactions. A study of the photodissociation of ketene

under jet-cooled conditions in the 193–215 nm wavelength range has shown
that bond fission to afford H atoms is a principal reaction.51 Acryloyl chloride
undergoes C–Cl bond fission on irradiation at 193 nm.52 The photodecarbon-
ylation of the cyclopropenones (54) occurs quantitatively on irradiation in
methanol solution to yield the corresponding alkynes. The quantum yield for
decarbonylation for the alkyl substituted derivatives is in the range 0.2–0.3,
while for the aryl derivatives f ¼ 0.7.53 A determination of the reaction
dynamics for the photodissociation of diphenylcyclopropenone has shown that
the dissociation occurs from the S2 state.54
Albini and co-workers55 have described the photochemical behaviour of

bicyclo[3.1.0]hexenones such as (55). The irradiation brings about the ring-
opening of the three-membered ring, and the resultant zwitterions are trapped
by the adjacent hydroxyl group to afford (56). Several examples were described.
Several derivatives of (57) have been studied as phototriggers for alcohols

and phenols. All of them are reactive, with varying quantum yields for the
release of the alcohol component from decomposition of the carbonate moiety.
The best of these was found to be (58), which releases phenol with a quantum
yield of 0.067.56 Dore and co-workers57 have described the photochemical
activity of the related coumarin derivative (59). Irradiation brings about release
of the aldehyde or ketone unit from the side chain affording (60).
2.2 b,c-Unsaturated Systems

2.2.1 The Oxa-Di-p-methane reaction and Related Processes. Interestingly,
some b,g-unsaturated ketones do not undergo 1,3-acyl shifts or the oxa-di-p-
methane rearrangement. An example of this is compound (61), which on
irradiation undergoes only a Norrish Type II hydrogen abstraction.58
The direct irradiation of the bicycloenones (62) results in a 1,3-acyl shift
followed by decarbonylation.59 The photochemical and thermal reactivity of
so-called o- and p-acylcyclohexadienones has been studied in a further attempt
to examine the mechanism of the photo-Fries process.60
Acetophenone-sensitized irradiation of the quinuclidinones (63) brings about

an oxa-di-p-methane rearrangement to afford (64) in 70% yield.61 Singh and
Lahiri62 have reported the odd photochemistry of the enone (65, R ¼ H, R1 ¼
Et). On irradiation of this compound at 300 nm in acetone, only a low yield of
the oxa-di-p-methane product (66) is obtained. The dominant product is (67),

formed by a 1,3-acyl migration. Interestingly, in the irradiation of (66) again in
acetone but using 254 nm light, the yield of the oxa di-p-product rises to 48%.
The rearrangement is also observed with (65, R ¼ R1 ¼ Me), which yields the
corresponding product (66). The rearrangement product (68) is formed on
acetone-sensitized irradiation of the bicyclo[2.2.2]octenone (69). The rearran-
gement is a standard 1,2-acyl shift of the oxa-di-p-methane type. The product is
obtained in 42% yield and has been used in an approach to the synthesis of
hirsutic acid.63 The oxa-di-p-methane rearrangement of the enediones (70) has
been studied in detail. The reactions shown in the Scheme 7 are typical of such
rearrangements, and the regiospecificity shown is determined by the stability of
the intermediate biradicals.
3 Photoreactions of Thymines and Related Compounds

3.1 Photoreactions of Pyridones. – The a-fission of the pyrimidone (71) has
been studied in a low temperature matrix. Irradiation under these conditions
leads to the formation of a conjugated isocyanate.64 A study has reported on
the control by hydrogen bonding of dimerization of pyridones such as (72).65a
A patent has been lodged dealing with the dimerization of 2-pyridone as an
inclusion compound with diphenic acid. This results in the formation of the
trans-anti-dimer (73) in 92% yield.65b The pyridone derivatives (74) also
undergo photochemical (4 þ 4)-dimerization to (75) on irradiation in the solid
Scheme 7
phase. Contrary to this behaviour is that observed in benzene when the

rearrangement product (76) is formed.65c
3.2 Photoreactions of Thymines, etc. – The photochemical decay paths for

some pyrimidines (thymine, 1,3-dimethylthymine, 1,3-dimethyluracil) in the gas
phase following laser excitation have been studied. Apparently, in contradiction
to how they behave in aqueous solution, the excited state molecules do not decay
back to the ground state immediately. The molecules exist in a dark state for tens
to hundreds of nanoseconds.66 Further study on the same systems has examined

the behaviour of the thymine-water complexes in the gas phase.67
Acetone-sensitized irradiation of (77) in acetonitrile solution affords the
intramolecular adduct (78) in 36% yield. The cycloaddition is quite specific and
affords the [5S,6S,7S]-lactone.68 Acetone-sensitized irradiation of the thymine
derivative (79) results in the formation of the cis,syn-dimer (80).69 A patent has
been filed dealing with the synthesis of (2 þ 2)-adducts such as (81).70 A study
of the conformational effects within the sugar moieties of (82) has been
investigated. Systems such as (82) are photochemically reactive and undergo
(2 þ 2)-cycloaddition to afford the adduct (83) on irradiation at 254 nm.71
Photodimerization of thymine in the crystalline form has been reported.72 A

study has examined theoretically the dimerization of pyrimidine units in DNA.
The results illustrate that thymine-thymine dimerization is more likely than
other combinations.73
Ethenobenzoquinazolines are obtained on irradiation of 5-fluoro-1,3-di-
methyuracil in the presence of 1-acetonaphthone. The product has the acetyl
group at the C–10 bridgehead carbon atom.74 The same uracil derivative
undergoes addition to naphthalene75 and other polyarenes. 6-Chloro-1,3-
dimethyuracil undergoes photochemical addition to various polycyclic arenes
and, for example, the addition to phenanthrene affords the adduct (84) where
the initial product has undergone elimination of HCl.76 6-Chloro-1,3-di-
methyuracil also undergoes 1,2-cycloaddition to naphthalenes to yield
naphthocyclobutapyrimidines. A 1,4-addition is involved in the photoaddition
of 1,3-dimethylthymine (85; R ¼ H) and some derivatives (R ¼ OMe, CF3 and
CH2OMe) to naphthalene. An ethenobenzoquinazoline (86) is formed by this
reaction.77
Mixtures of coumarin and thymine undergo cycloaddition on irradiation in

the presence of a molecular recognition catalyst. The reaction affords two cross
adducts identified as the cis,syn- and the cis,anti-adducts.78 1,3-Dimethyluracil
is reported to form oxetanes on irradiation in the presence of ketones.79 An
electron transfer process can be used to regenerate the uracil from the oxetane.
A study of the triplet-state induced splitting of cyclobutane thymine dimers has
been carried out using 9,10-anthraquinone-2-sulphonate as the sensitizer. An

electron-transfer mechanism is involved.80
4 Photochemistry of Dienones
4.1 Cross-conjugated Dienones. – The bicyclic dienone (87) undergoes a

reversible colour change on irradiation as inclusion crystals.81 Cross-conju-
gated cyclohexadienones provide a good path to the corresponding ketenes on
irradiation. When this is carried out in the presence of a nucleophile, the ketene
can be trapped as the corresponding amide. A series of linked, cross-conjugated
bis-cyclohexadienones have been studied. These compounds undergo ring
opening to afford the corresponding bis-ketenes, which again can be trapped
efficiently with amines, etc.82 Albini and co-workers83 have investigated the
photochemical reactivity of the dienones (88). The outcome of the reactions is
wavelength dependent. Irradiation at 254 nm or 366 nm converts (88) into the
corresponding lumi-products (89). Irradiation at 310 nm, however, brings
about loss of the C–20 side chain by an efficient a-cleavage. This yields products
such as (90).
The marine deoxytridachione (91) converts to the rearrangement products

(92) in a reaction that is thought to be photochemically activated. In an attempt
to justify this hypothesis, the polyenes (93) were synthesized and their photo-
chemical behaviour examined. Irradiation demonstrated that there was an
initial E,Z-isomerization to afford (94), which then cyclizes to (95). This
product can then be photochemically converted into the bicyclic product
(96).84 Such reactivity is in support of the original hypothesis. The photo-
chemical decomposition of nalidixic acid (97) in methanol solution in the
presence and absence of air has been studied.85
The irradiation of the bromotropones in the presence of 1,10-dicyanoan-

thracene affords novel products. The conditions used for the irradiations excite
the anthracene and are carried out in methylene chloride or methylene chloride-
acetonitrile solution. The compound (98a) affords the two adducts (99) and
(100), while (98b) gives (101) and (102) in the yields shown.86 The polyhalo-
genated tropones (103) undergo the usual ring closure to afford (104) on
irradiation in solution.87 Colchicine (105) also undergoes this photochemical

transformation to yield the b-(106) and the g-(107) isomers.88
4.2 Linearly Conjugated Dienones. – Two reaction modes have been detected
following a study of the photoreactivity of 4,6-dimethyl-a-pyrone in a matrix.
Irradiation with l 4 315 nm brings about both ring-opening to yield a ketene
and valence isomerization to produce 1,5-dimethyl-2-oxa-3-oxobicyclo[2.2.0]-
hex-5-ene.89,90
A further study has examined the photobehaviour of a-pyrone on irradiation

at wavelengths 4285 nm in a matrix. The most efficient reaction observed is a
Norrish Type I ring-opening to afford the usual conjugated aldehydoketene.
Further irradiation brings about isomerization of the double bonds to afford
the Z-isomer. Ring-opening is accompanied by isomerization to the corre-
sponding Dewar structure, while irradiation at wavelengths 4235 nm gives
evidence for the formation of cyclobutadiene.91
5 1,2-, 1,3- and 1,4-Diketones
5.1 Reactions of 1,2-Diketones and other 1,2-Dicarbonyl Compounds. – 1,2-

Dicarbonyl compounds such as glyoxal and biacetyl have been irradiated under
direct sunlight.92 A study has examined the wavelength dependence for fission
of glyoxal into the CHO radical on irradiation in the 290–420 nm range.93 a-
Fission is the principal photochemical reaction of vicinal cyclic tricarbonyl
compounds such as indanetriones.94
ab initio Calculations on the photochemical decomposition of oxalyl chloride
have indicated that, in the first excited state, the first fission is the release of a
chlorine atom,95 but irradiation of oxalyl chloride at 193 nm results in
decarbonylation.96 The irradiation of dipropargyl oxalate at 193 nm provides
a new path to propargyl radicals in the gas phase.97
Both H abstraction and desilylation compete on irradiation of the ketoamide
(108, M ¼ Si). Some of the products formed are illustrated in the Scheme 8.
Irradiation of the stannyl derivative (108, M ¼ Sn) involves a SET-destannyla-
tion pathway.98 The nature of the substituent on the aryl group in (109) appears
to control the outcome of the photochemical reaction. Thus for (109, Y ¼ CN
or CF3), irradiation brings about release of the phenol moiety, while for (109, Y
¼ Me or MeO) rearrangement occurs to yield (110).99 Irradiation of the
complex ketoamide (111) in methanol brings about cleavage of the N–CO
bond. Several model systems were also studied.100
Scheme 8
Triplet 1-acetyl isatin (112) undergoes hydrogen abstraction from a variety of

aldehydes. Some of the products, shown in Scheme 9, result from coupling of
the radicals (113) formed by the hydrogen abstraction path.101
Scheme 9
5.2 Reactions of 1,3-Diketones. – A tuneable laser has been used to study the
photoisomerization of acetylacetone in a nitrogen matrix at 10 K.102 Organero
and Douhal103 have reported a temperature effect on non-radiative decay
processes within 1-hydroxy-2 0 -acetonaphthone. Viscosity and polarity effects

were also studied.
5.3 Reactions of 1,4-Diketones. – The indenylidenedione (114) is photochro-

mic on irradiation in the crystalline phase. When the dideuterio isomer is used,
the photochromic material is extremely slow to revert to the dione in the
dark.104 The diones (115) undergo efficient conversion into the isobenzofur-
anones (116) on irradiation.105 Irradiation of (117) at 308 nm in a nitrogen
matrix brings about CO and CO2 loss to afford the benzyne (118).106
A route to cyclic peptide mimetics has been developed using the SET-induced
photochemical cyclization of the phthalimide derivatives (119). This process
affords the cyclized compounds (120) in excellent yields (85–91%).107 Hydroxy-
phthalimidines are the products formed from the photochemical decarboxy-
lation of a series of alkyl carboxylates in the presence of N-substituted
phthalimides.108 The photochemical addition of a-silyl electron-donor systems,
such as Et2NCH2SiMe3, to N-methylthiophthalimide takes place in polar
solvents such as acetonitrile.109
Thio ether N-substituted 4,5-dimethoxyphthalimides undergo strong fluor-

escence quenching by an intramolecular electron transfer from the substituents
on the nitrogen.110 Suau et al.111 have studied further the SET-induced
photochemical reactions of the phthalimide anion. Under conditions of high
NaOH concentration, the predominant reaction is (2 þ 2)-cycloaddition to
afford products such as (121). At lower NaOH concentrations, N-attachment is
the dominant reaction, affording (122). This reactivity is shown in Scheme 10.
The N-attachment reaction has been utilized to synthesize a series of derivatives
(123). This provides a reasonable route to the synthesis of phenylethylamine
derivatives. Biczok et al.112 have studied the pathways available for energy
dissipation from the excited ion pairs formed between N-methyl-3-hydroxy-
naphthalimide and 1-methylimidazole. Some important fragmentation reac-
tions of aminium radicals have been discussed.113
Scheme 10
A (2 þ 2)-photoadduct is formed on irradiation of 2,3-dimethylmaleic

anhydride with 3,4-dimethyl-1-phenylphosphole.114 The photocycloaddition
of maleic anhydride derivatives (124) to the alkene moiety in (125) affords
the adducts (126) by a straightforward (2 þ 2)-addition.115 The (2 þ 2)-
photoadducts (127) are readily produced by the dimerization of the corre-
sponding maleic anhydrides in ethyl acetate solution.116 The intramolecular
photochemical cyclization of the succinimide derivative (128) is a key step in the
new synthetic approach to the tetracyclic fragment of neotuberostemonine.117
A detailed account of the (2 þ 2)-photocycloaddition reactions of homo-

quinones has been published. The addition reactions afford regio and exo,endo
isomers of tricyclic diones. The major product is thought to arise from the more
stable triplet 1,4–biradical intermediate.118 A review has reported on the
addition of alkenes and alkynes to the enone system of homobenzoquinones.119
Dibromo-9-(3-oxo-3-phenylprop-1-ynyl)-[9H]-fluoren-9-yl-3-fluoren-9-ylidene-
1-phenylpropenone is photochromic in the crystalline state.120
5.4 Fulgides and Fulgimides. – Calculations have been carried out in an

examination of the mechanism of fulgide photochromism121 and have dealt
with the absorptivities of photochromic indolylfulgides.122 A patent has been
lodged dealing with the synthesis of photochromic indolylfulgides.123
The oxalylfulgides (129) have been prepared and studied. These photochro-
mic yellow dyes undergo ring closure in the conventional manner. The quantum
yields for the process and the solvent dependency results are shown below the
structures.124 A double Stobbe condensation of 3,5-dimethoxybenzaldehyde
with succinic anhydride affords the fulgide (130). This is photochemically
reactive and undergoes cyclization to afford a pink cyclic form on irradiation
at 366 nm.125
Some new pyrrylfulgide derivatives have been studied as potential optical

storage materials.126 The photochromic properties of (Z)-4-oxazolylfulgim-
ide{(Z)-1-benzyl-4-isopropylidene-3-[1-(2-aryl-5-methyloxazolyl)ethylidene]te-
trahydrofuran-2,5-dione}, a new class of fulgimide, have been examined.127
A patent application has described the synthesis and photochemical reactiv-
ity of the fulgimide derivatives (131).128 Fulgimides can be prepared by
conversion of the fulgides (132) and (133). The resultant products shown
photochromic properties.129 Some new derivatives of fulgimides have been
reported with thieno[3,2-b]pyrrole fragments attached to the maleimide.130
6 Quinones
6.1 p-Quinones. – Goerner131 has demonstrated that the yield of semiquinone

radicals is low in the absence of hydrogen donating solvents. He notes that the
quantum yield for decomposition is substantial in aqueous solution. A detailed
account of the photohydroxylation reactions of 1,4-benzoquinone in aqueous
solution has been published.132 The photochemical cyclization of some Diels-
Alder adducts of benzo-1,4-quinones has been described. This has provided a
path to complex molecules such as 3-bromotetracyclo[5.3.1.02,6.04,8]undec-
10(12)-ene-9,11-dione.133 A biradical has been identified as the key intermediate
in the photocyclization of phenylbenzoquinone.134 A charge-transfer complex
is formed initially on irradiation of 2-chloro-5-methoxybenzo-1,4-quinone in
the presence of triethylamine and various solvents.135 2-Chloro-5-methoxyben-
zo-1,4-quinone also undergoes addition to arylalkynes to afford oxetenes. The
mechanism of this addition reaction was studied.136 A hydrogen abstraction is
involved in the photochemical reactions of chloranil with b-diketones.137
The rate of photochemical transformation of naphtho-1,4-quinone into 1,4-
dihydroxynaphthalene and 5- and 7-hydroxynaphthoquinone is high in acidic
media. The rate of transformation is slowed dramatically at higher pH.138 A
study of the bichromophoric quinostilbene derivatives (134) has examined the
donor-acceptor properties of the molecules.139
Studies of electron transfer between 1,4-dihydroxy-9,10-anthraquinone and

aromatic amines has shown that quenching of the quinone fluorescence is the
result.140 The azaquinone imine (135) undergoes photoarylotropic rearrange-
ment on irradiation.141
References
1. (a) K. Kakiuchi, Kokagaku, 2002, 33, 126; (b) K. Kakiuchi, Chem. Abstr., 2003,
139, 36089.
2. I. Turowska-Tyrk, K. Grzesniak, E. Trzop and T. Zych, J. Solid State Chem.,
2003, 174, 459.
3. H. Saito, T. Mori, T. Wada and Y. Inoue, J. Am. Chem. Soc., 2004, 126, 1900.
4. S. Furumi, A. Otomo, S. Yokoyama and S. Mashiko, Thin Solid Films, 2003,
438–439, 85.
5. S.D.M. Atkinson, M.J. Almond, S.J. Hibble, P. Hollins, S.L. Jenkins, M.J. Tobin
and K.S. Wiltshire, Phys. Chem. Chem. Phys., 2003, 6, 4.
6. (a) K. Sugiyama, H. Takayanagi and E. Noguchi, Nihon Daigaku Seisankogakubu
Kenkyu Hokoku, A: Rikokei, 2003, 36, 49; (b) K. Sugiyama, H. Takayanagi and
E. Noguchi, Chem. Abstr., 2004, 140, 59220.
7. Y. Ito, T. Kitada and M. Horiguchi, Tetrahedron, 2003, 59, 7323.
8. (a) V. Darcos, K. Griffith, X. Sallenave, J.-P. Desvergne, C. Guyard-Duhayon,
B. Hasenknopf and D.M. Bassani, Photochem. Photobiol. Sci., 2003, 2, 1152;
(b) V. Darcos, K. Griffith, X. Sallenave, J.-P. Desvergne, C. Guyard-Duhayon,
B. Hasenknopf and D.M. Bassani, Chem. Abstr., 2004, 140, 198902.
9. (a) J.-J. Wang, J.-G. Yin, X.-R. Wu, M.Y. Zhao, A. Mori and T. Toshihide, Youjii
Huaxue, 2003, 23, 1120; (b) J.-J. Wang, J.-G. Yin, X.-R. Wu, M.Y. Zhao, A. Mori
and T. Toshihide, Chem. Abstr., 2004, 140, 199467.
10. I. Turowska-Tyrk, Acta Cryst. Sect. B, 2003, B59, 670.
11. M.C. de la Torre, I. Garcia and M.A. Sierra, J. Org. Chem., 2003, 68, 6611.
12. J.R. Williams, J.B. Ma, P. Wepplo and R.A. Paclin, J. Org. Chem., 2004, 69, 1730.
13. (a) G. Mehta, P. Ghosh and K. Sreenivas, ARKIVOC, 2003, 92; (b) G. Mehta,
P. Ghosh and K. Sreenivas, Chem. Abstr., 2003, 139, 180202.
14. (a) P. de March, M. Figueredo, J. Font, J. Raya, A. Alvarez-Larena and
J.F. Piniella, J. Mol. Struct., 2003, 648, 69; (b) P. de March, M. Figueredo,
J. Font, J. Raya, A. Alvarez-Larena and J.F. Piniella, Chem. Abstr., 2003, 139,
21811.
15. H.I. Omar, Y. Odo, Y. Shigemitsu, T. Shimo and K. Somekawa, Tetrahedron,
2003, 59, 8099.
16. (a) K. Tsutsumi, F. Katsunori, T. Ikki, S. Hiroaki, T. Shintani, T. Morimoto and
K. Kakiuchi, Chirality, 2003, 15, 504; (b) K. Tsutsumi, F. Katsunori, T. Ikki,
S. Hiroaki, T. Shintani, T. Morimoto and K. Kakiuchi, Chem. Abstr., 2004, 140,
111048.
17. T. Shintani, K. Kusabiraki, A. Hattori, A. Furutani, K. Tsutsumi, T. Morimoto
and K. Kakiuchi, Tetrahedron Lett., 2004, 45, 1849.
18. E. Garcia-Exposito, A. Alvarez-Larena, V. Branchadell and R. M. Ortuno, J. Org.
Chem., 2004, 69, 1120.
19. K. Tsutsumi, H. Nakano, A. Furutani, K. Endou, A. Merpuge, T. Shintani,
T. Morimoto and K. Kakiuchi, J. Org. Chem., 2004, 69, 785.
20. L. Meyer, N. Alouane, K. Schmidt and P. Margaretha, Can. J. Chem., 2003, 81, 417.
21. D. Madhavan and K. Pitchumani, Photochem. Photobiol. Sci., 2002, 1, 991.
22. E.S. Greenwood, P.B. Hitchcock and P.J. Parsons, Tetrahedron, 2003, 59, 3307.
23. (a) S. Ota, M. Yamashita, A. Tada and K. Matsumoto, Jpn. Kokai Tokkyo Koho.
JP, 2003, 128, 662; (b) S. Ota, M. Yamashita, A. Tada and K. Matsumoto, Chem.
Abstr., 2003, 138, 337886.
24. W.G. Skene, E. Couzigne and J.-M. Lehn, Chem.-Eur. J., 2003, 9, 5560.
25. X.L. Yu, D. Scheller, O. Rademacher and T. Wolff, J. Org. Chem., 2003, 68, 7386.
26. T. Wolff and H. Goerner, Phys. Chem. Chem. Phys., 2003, 6, 368.
27. M. Fujiwara, K. Shiokawa, N. Kawasaki and Y. Tanaka, Adv. Functional Mat.,
2003, 13, 371.
28. (a) F. Zhu, T. Ngai, Z. Xie and C. Wu, Macromolecules, 2003, 36, 7405; (b) F. Zhu,
T. Ngai, Z. Xie and C. Wu, Chem. Abstr., 2003, 139, 308081.
29. A.-H. Chen, W.-B. Kuo and C.-W. Chen, J. Chin. Chem. Soc. (Taipei, Taiwan),
2003, 50, 123.
30. F.R. Cibin, N. Di Bello, G. Doddi, V. Fares, P. Mencarelli and E. Ullucci,
Tetrahedron, 2003, 59, 9971.
31. M. Kemmler and T. Bach, Angew. Chem. Int. Edn., 2003, 42, 4824.
32. B.T.B. Hue, J. Dijkink, S. Kuiper, K.K. Larson, F.S. Guziec, jun., K. Gobitz,
J. Fraanje, H. Schenk, J.H. van Maarseveen and H. Hiemstra, Org. Biomol. Chem.,
2003, 1, 4346.
33. (a) K. Krohn and J. Wunnschhofer, ARKIVOC, 2002, 19; (b) K. Krohn and
J. Wunnschhofer, Chem. Abstr., 2003, 138, 346305.
34. S. Sundaryono, A. Nourmamode, C. Gardrat, S. Grelier, G. Bravic, D. Chasseau
and A. Castellan, Photochem. Photobiol. Sci., 2003, 2, 914.
35. S. Pattanaargson, T. Munhapol, N. Hirunsupachot and P. Luangthongaram,
36. Y. Minoura, N. Nagashima, S. Kudoh and M. Nakata, J. Phys. Chem. A, 2004,
108, 2353.
37. H. Ikeda, F. Tanaka, T. Miyashi, K. Akiyama and S. Tero-Kubota, Eur. J. Org.
Chem., 2004, 1500.
38. H. Ikeda, F. Tanaka, K. Akiyama, S. Tero-Kubota and T. Miyashi, J. Am. Chem.
Soc., 2004, 126, 414.
39. (a) V.V. Eremin, Yu.Yu. Pakhomova, I.I. Yurkov and N.E. Kuz’menko, Zhur. Fiz.
Khim., 2003, 77, 349; (b) V.V. Eremin, Yu.Yu. Pakhomova, I.I. Yurkov and N.E.
Kuz’menko, Chem. Abstr., 2003, 139, 69387.
40. W.S. Harper and E.R. Gaillard, Photochem. Photobiol., 2003, 78, 298.
41. N.E. Polyakov, T.V. Leshina, E.O. Hand, A. Petrenko and L.D. Kispert,
42. (a) J. Danielsson and A. Laaksonen, Chem. Phys. Lett., 2003, 370, 625;
(b) J. Danielsson and A. Laaksonen, Chem. Abstr., 2003, 138, 409206.
43. M.S. Bjelakovic, V.D. Pavlovic, M.M. Dabovic and L.B. Lorenc, J. Serb. Chem.
Soc., 2003, 68, 303.
44. F. Bargiggia and O. Piva, Tetrahedron: Asymmetry., 2003, 14, 1819.
45. Y. Norikane, N. Nakayama, N. Tamaoki, T. Arai and U. Nagashima, J. Phys.
Chem. A, 2003, 107, 8659.
46. (a) K. Kaneda and T. Arai, Photochem. Photobiol. Sci., 2003, 2, 402; (b) K. Kaneda
and T. Arai, Chem. Abstr., 2003, 139, 164470.
47. Y. Chiang, A.J. Kresge and H.Q. Zhan, Can. J. Chem., 2003, 81, 607.
48. K. Tsuchii, M. Doi, T. Hirao and A. Ogawa, Angew. Chem. Int. Edn., 2003, 42, 3490.
49. (a) N. Hoffmann and H. Goerner, Chem. Phys. Lett., 2004, 383, 451;
(b) N. Hoffmann and H. Goerner, Chem. Abstr., 2004, 140, 198891.
50. (a) R. Alibes, J.L. Bourdelande, A. Gregori, J. Font, A. Rustullet and T. Parella,
J. Carbohydrate Chem., 2003, 22, 501; (b) R. Alibes, J.L. Bourdelande, A. Gregori,
J. Font, A. Rustullet and T. Parella, Chem. Abstr., 2004, 140, 146376.
51. E.J. Feltham, R.H. Qadiri, E.E.H. Cottrill, P.A. Cook, J.P. Cole, G.G. Balint-Kurti
and M.N.R. Ashfold, J. Chem. Phys., 2003, 119, 6017.
52. D.E. Szpunar, J.L. Miller, L.J. Butler and F. Qi, J. Chem. Phys., 2004, 120, 4223.
53. A.P. Vladimir and V.V. Popik, J. Org. Chem., 2003, 68, 7833.
54. S. Takeuchi and T. Tahara, J. Chem. Phys., 2004, 120, 4768.
55. A. Ricci, E. Fasani, M. Mella and A. Albini, Tetrahedron, 2004, 60, 115.
56. A.Z. Suzuki, T. Watanabe, M. Kawamoto, K. Nishiyama, M. Ishii, M. Iwamura
and T. Furuta, Org. Lett., 2003, 5, 4867.
57. M. Lu, O.D. Fedoryak, B.R. Moister and T.M. Dore, Org. Lett., 2003, 5, 2119.
58. C.J. Mortko, H. Dang, L.M. Campos and M.A. Garcia-Garibay, Tetrahedron
Lett., 2003, 44, 6133.
59. O. Arjona, R. Medel, J. Plumet and J.K. Rojas, Rev. Soc. Quim. Mexico, 2003,
47, 227.
60. T. Mori, M. Takamoto, H. Saito, T. Furo, T. Wada and Y. Inoue, Chem. Lett.,
2004, 256.
61. C.K. McLure, A.J. Kiessling and J.S. Link, Org. Lett., 2003, 5, 3811.
62. V. Singh and S. Lahiri, Tetrahedron Lett., 2003, 44, 4239.
63. V. Singh, D.K. Tosh and S.M. Mobin, Tetrahedron Lett., 2004, 45, 1729.
64. L. Lapinski, H. Rostkowska, A. Khvorostov, R. Fausto and M.J. Nowak, J. Phys.
Chem. A, 2003, 107, 5913.
65. (a) A. Matsumoto, K. Maeda and T. Arai, J. Phys. Chem. A, 2003, 107, 10039;
(b) M. Yagi and F. Toda, Jpn. Kokai Tokkyo Koho. Jp 2004 99,442 (Chem. Abstr.,
2004, 140, 303542); (c) S. Kohmoto, T. Noguchi, H. Masu, K. Kishikawa,
M. Yamamoto and K. Yamaguchi, Org. Lett., 2004, 6, 683.
66. Y.G. He and C.Y. Wu and. Kong, J. Phys. Chem. A, 2003, 107, 5145.
67. Y.G. He, C.Y. Wu and W. Kong, J. Phys. Chem. A, 2004, 108, 943.
68. A. Agocs, G. Batta, J. Jeko and P. Herczegh, Tetrahedron: Asymmetry, 2004
15, 283.
69. J.U.O. Mayo, M. Thomas, C. Saintome and P. Clivio, Tetrahedron, 2003, 59, 7377.
70. P. Clivio, M. Thomas, M. Ortiz and U. Javier, FR 2836145, 2002.
71. T. Ostrowski, J.C. Maurizot, M.T. Adeline, J.L. Fourrey and P. Clivio, J. Org.
Chem., 2003, 68, 6502.
72. (a) V.L. Rapoport and V.M. Malkin, Khim Fiz., 2003, 22, 3; (b) V.L. Rapoport and
V.M. Malkin, Chem. Abstr., 2003, 139, 221454.
73. B. Durbeej and L.A. Eriksson, Photochem. Photobiol., 2003, 78, 159.
74. (a) K. Ohkura, S. Tatsuyuki, A. Sakushima, K. Nishijima, Y. Kuge and K. Seki,
Heterocycles, 2002, 58, 595; (b) K. Ohkura, S. Tatsuyuki, A. Sakushima,
K. Nishijima, Y. Kuge and K. Seki, Chem. Abstr., 2003, 138, 321265.
75. (a) K. Ohkura, T. Sugaoi, T. Ishihara, K. Aizawa, K. Nishijima, Y. Kuge and
K. Seki, Heterocycles, 2003, 61, 377; (b) K. Ohkura, T. Sugaoi, T. Ishihara,
K. Aizawa, K. Nishijima, Y. Kuge and K. Seki, Chem. Abstr., 2004, 140, 181407.
76. (a) K. Ohkura, S. Uchiyama, M. Sato, J.M. Diakur and K.-I. Seki, Heterocycles,
2003, 59, 459; (b) K. Ohkura, S. Uchiyama, M. Sato, J.M. Diakur and K.-I. Seki,
Chem. Abstr., 2003, 139, 149597.
77. (a) K. Ohkura, T. Ishihara, Y. Nakata and K. Seki, Heterocycles, 2004, 60, 213;
(b) K. Ohkura, T. Ishihara, Y. Nakata and K. Seki, Chem. Abstr., 2004, 140,
181408.
78. (a) O. Murai, H. Ikeda and Y. Nakamura, Heterocyclic Commun., 2002, 8, 469;
(b) O. Murai, H. Ikeda and Y. Nakamura, Chem. Abstr., 2003, 138, 409174.
79. Q.H. Song, X. Hei, Z. Xu, X. Zhang and Q. Guo, Bioorganic Chem., 2003, 31, 357.
80. Z.Y. Sheng, Y. Pan, L.Q. Yan, X.M. Hei, Z.Y. Guo, J.H. Dai, Q.H. Song and
S.Q. Yu, J. Photochem. Photobiol. A: Chem., 2004, 161, 99.
81. K. Tanaka, T. Watanabe and M. Kato, J. Chem. Res., 2003, S, 535.

82. (a) T.W. Kwon, S.J. Song, U. Yong and S.K. Chung, Bull. Korean Chem. Soc.,
2003, 24, 229; (b) T.W. Kwon, S.J. Song, U. Yong and S.K. Chung, Chem. Abstr.,
2003, 139, 28552.
83. A. Ricci, E. Fasani, M. Mella and A. Albini, J. Org. Chem., 2003, 68, 4361.
84. S. Bruckner, J.E. Baldwin, J. Moses, R.M. Adlington and A.R. Cowley,
85. H. Park, O. Park, H. Lee, J. Seo and K. Bark, Bull Korean Chem. Soc., 2003, 24, 1618.
86. A. Mori, H. Kawakami, N. Kato, S.-P. Wu and H. Takeshita, Org. Biomol. Chem.,
2003, 1, 1730.
87. Y. Lou, Y.G. He, J.T. Kendall and D.M. Lemal, J. Org. Chem., 2003, 68, 3891.
88. L. Bussotti, I. Cacelli, M. D’Auria, P. Foggi, G. Lesma, A. Silvani and V. Villani,
J. Phys. Chem. A, 2003, 107, 9079.
89. S. Breda, L. Lapinski, I. Reva and R. Fausto, J. Photochem. Photobiol. A: Chem.,
2004, 162, 139.
90. (a) S. Breda, L. Lapinski, R. Fausto and M.J. Nowak, Phys. Chem. Chem. Phys.,
2003, 5, 4527; (b) S. Breda, L. Lapinski, R. Fausto and M.J. Nowak, Chem. Abstr.,
2004, 140, 76745.
91. S. Breda, I. Reva, L. Lapinski and R. Fausto, Phys. Chem. Chem. Phys., 2004
6, 929.
92. (a) B. Klotz, F. Graedler, S. Sorensen, I. Barnes and K.-H. Becker, Ber.-Berg.
Univers, Physikal. Chem., 2000, 60; (b) B. Klotz, F. Graedler, S. Sorensen, I. Barnes
and K.-H. Becker, Chem. Abstr., 2003, 139, 237532.
93. Y.Q. Chen and L. Zhu, J. Phys. Chem. A, 2003, 107, 4643.
94. (a) J. Tatsugi, Kokagaku, 2002, 33, 22; (b) J. Tatsugi, Chem. Abstr., 2003, 139, 36086.
95. (a) N. Dai and Z. Li, Sci, China, Ser. B: Chem., 2003, 46, 19; (b) N. Dai and Z. Li,
Chem. Abstr., 2003, 139, 21794.
96. C.-Y. Wu, Y.-P. Lee and N.S. Wang, J. Chem. Phys., 2004, 120, 6957.
97. B.R. Giri, H. Hippler, M. Olzmann and A.N. Unterreiner, Phys. Chem. Chem.
Phys., 2003, 5, 4641.
98. R.T. Wang, C.F. Chen, E. Duesler, P.S. Mariano and U.C. Yoon, J. Org. Chem.,
2004, 69, 1215.
99. C.C. Ma and M.G. Steinmetz, Org. Lett., 2004, 6, 629.
100. M.A.R.C. Bulusu, P. Waldstatten, T. Tricotett and G. Schulz, Tetrahedron Lett.,
2004, 45, 2523–2527.
101. Y. Zhang, L. Wang, Y. Zhu and J.-H. Xu, Eur. J. Org. Chem., 2004, 527.
102. (a) S. Coussan, C. Manca, Y. Ferro and P. Roubin, Chem. Phys. Lett., 2003, 370,
118; (b) S. Coussan, C. Manca, Y. Ferro and P. Roubin, Chem. Abstr., 2003, 138,
409191.
103. (a) J.A. Organero and A. Douhal, Chem. Phys. Lett., 2003, 381, 759;
(b) J.A. Organero and A. Douhal, Chem. Abstr., 2004, 140, 110994.
104. K. Tanaka, Y. Yamamoto, H. Takano and M.R. Caira, Chem. Lett., 2003, 680.
105. M. Kapoor, S.N. Dhawan, S. Mor, S.C. Bhatia, S.C. Gupta and M.S. Hundal,
Tetrahedron, 2003, 59, 5027.
106. T. Sato, H. Niino and A. Yabe, J. Am. Chem. Soc., 2003, 125, 11936.
107. U.C. Yoon, Y.X. Jin, S.W. Oh, C.H. Park, J.H. Park, C.F. Campana, X.L. Cai,
E.N. Duesler and P.S. Mariano, J. Am. Chem. Soc., 2003, 125, 10664.
108. (a) M. Oelgemoller, P. Cygon, J. Lex and A.G. Griesbeck, Heterocycles, 2003, 59,
669; (b) M. Oelgemoller, P. Cygon, J. Lex and A.G. Griesbeck, Chem. Abstr., 2003,
139, 85195.
109. (a) U.C. Yoon, S.W. Oh, S.C. Moon and G. Tae, J. Photosci., 2002, 9, 17;
(b) U.C. Yoon, S.W. Oh, S.C. Moon and G. Tae, Chem. Abstr., 2003, 138, 385246.
110. A.G. Griesbeck and S. Schieffer, Photochem. Photobiol. Sci., 2003, 2, 113.
111. R. Suau, R. Garcia-Segura, C. Sanchez-Sanchez, E. Perez-Inestrosa and
A.M. Pedraza, Tetrahedron, 2003, 59, 2913.
112. (a) L. Biczok, P. Valat and V. Wintgens, Photochem. Photobiol. Sci., 2003, 2, 230;
(b) L. Biczok, P. Valat and V. Wintgens, Chem. Abstr., 2003, 139, 44099.
113. U.C. Yoon and P.S. Mariano, J. Photosci., 2003, 10, 89.
114. F. Vargas, C. Rivas, A. Fuentes, K. Carbonell and R. Rodriguez, J. Photochem.
Photobiol. A: Chem., 2004, 162, 63.
115. (a) H. Suzuki, S. Tsuji, H. Nawata and T. Nihei, Jpn. Kokai Tokkyo Koho. JP,
2003, 119, 199; (b) H. Suzuki, S. Tsuji, H. Nawata and T. Nihei, Chem. Abstr.,
2003, 138, 321271.
116. (a) H. Suzuki, Y. Otsuka and M. Ishikawa, Jpn. Kokai Tokkyo Koho. JP, 2003,
192, 685; (b) H. Suzuki, Y. Otsuka and M. Ishikawa, Chem. Abstr., 2003, 139,
101519.
117. K.I. Booker-Milburn, P. Hirst, J.P.H. Charmant and L.H.J. Taylor, Angew. Chem.
Int. Edn., 2003, 42, 1642.
118. (a) K. Kokubo and T. Oshima, Kokagaku, 2002, 33, 28; (b) K. Kokubo and
T. Oshima, Chem. Abstr., 2003, 139, 36087.
119. (a) K. Kokubo and T. Oshima, Yuki Gosei Kagaku Kyokaishi, 2003, 61, 360;
(b) K. Kokubo and T. Oshima, Chem. Abstr., 2003, 139, 149354.
120. K. Tanaka, A. Tomomori and J.L. Scott, CrystEngComm., 2003, 5, 147.
121. S. Li, Z. Li and W. Feng, Beijing Huagong Daxue Xuebao, Ziran Kexueban, 2003,
30, 62.
122. R. Zalesny, W. Bartkowiak and J. Leszczynski, J. Lumin., 2003, 105, 111.
123. P.M. Rentzepis and A. Dvornikov, US 6693201.
124. R. Matsushima, H. Morikane and Y. Kohno, Chem. Lett., 2003, 302.
125. A.M. Asiri, J. Photochem. Photobiol. A: Chem., 2003, 159, 1.
126. M. Lei, B. Yao, Y. Chen, H. Yi, W. Yong, M. Yingli, N. Menke, Y. Zheng,
C. Wang, M. Fan and G. Chen, Chin. Sci. Bull., 2003, 48, 1548.
127. J. Xiao, Y. Han, Y. Chen, W. Li and M. Fan, Chin. J. Chem., 2004, 22, 100.
128. M. Fan, L. Zhao, Y. Ming and W. Zhao, CN 1,353,162; Chem. Abstr., 2003, 139,
92825.
129. B. Otto and K. Ruck-Braun, Eur. J. Org. Chem., 2003, 2409.
130. M.M. Krayushkin, V.N. Yarovenko, S.L. Semenov, I.V. Zavarzin, A.Yu. Martynkin
and B.M. Uzhinov, Russ. Chem. Bull., 2003, 52, 1814.
131. H. Goerner, J. Phys. Chem. A, 2003, 107, 11587.
132. J. von Sonntag, E. Mvula, K. Hildenbrand and C. von Sonntag, Chem.-Eur.
J., 2004, 10, 440.
133. U. Sudhir, B. James, S. Joly and M.S. Nair, Res. Chem. Intermed., 2003, 29, 523.
134. N. Chattopadhyay, C. Serpa, L.G. Arnaut and S.J. Formosinho, Indian J. Chem.,
Sect. A., 2003, 42A, 1827.
135. (a) H.-L. Guo, B.-Z. Yan and X.Y. Guo, Youji Huaxue, 2003, 23, 288;
(b) H.-L. Guo, B.-Z. Yan and X.Y. Guo, Chem. Abstr., 2003, 139, 68839.
136. (a) X.Y. Wang, B.Z. Yan and T. Wang, Chin. Chem. Lett., 2003, 14, 270;
(b) X.Y. Wang, B.Z. Yan and T. Wang, Chem. Abstr., 2003, 139, 149234.
137. (a) H.-l. Guo, B.-z. Yan and M.-c. Wang, Gangguang Kexue Yu Guang Huaxue,
2003, 21, 95; (b) H.-l. Guo, B.-z. Yan and M.-c. Wang, Chem. Abstr., 2003, 139,
84912.
138. O. Brahamia and C. Richard, Photochem. Photobiol. Sci., 2003, 2, 1038.

139. Y. Sutovsky, G.I. Likhtenshtein and S. Bittner, Tetrahedron, 2003, 59, 2939.
140. M. Kumbhakar, S. Nath, M.C. Rath, T. Mukherjee and H. Pal, Photochem.
Photobiol., 2004, 79, 1.
141. (a) N.T. Sokolyuk and L.P. Pisulina, Russ. J. Org. Chem., 2002, 38, 1212;
(b) N.T. Sokolyuk and L.P. Pisulina, Chem. Abstr., 2003, 138, 353821.
Photochemistry of Alkenes, Alkynes and
Related Compounds
Dundee, UK
1 Reactions of Alkenes
A review of photochemistry carried out in ionic liquids1 and a monograph

dealing with a variety of aspects of photochromism have been published.2
Reviews have also highlighted the photosensitized enantiodifferentiating isomer-
ization of cycloalkenes other than cyclooctene3 and the area of asymmetric
photochemistry in general.4 Mechanisms for the photosensitized isomerization of
alkenes have been discussed5 and calculations have been carried out to assess the
electron-transfer processes in the tetramethylethene-tetracyanoethene system.6
1.1 cis, trans-Isomerization. – The influence of sudden polarization on the

photochemical behaviour of ethene has been studied.7 Changes in the absorp-
tion spectra of the styrenes (1) are reported as evidence for the hula-twist
isomerization of the compounds. The reactions are carried out at 1961C in an
EPA glass.8 Lewis and Zuo9 have described the application of non-linear fitting
of lifetime and quantum yield data for styrene derivatives such as 2-vinyl-
biphenyls and 1,3-diphenylpropenes, and they10 have shown that syn-2-vinyl-
biphenyls undergo conformer-specific photochemical cyclization to afford
dihydrophenanthrenes. A highly selective isomerization of some naphthylidene
derivatives has been reported. The molecules in question have both electron
donating and electron withdrawing groups that lead to a CT excited singlet
state.11 The components of the fluorescence spectra of trans-1-(2-naphthyl)-1-
phenylethene in benzene solution have been obtained by using variation of the
excitation wavelength.12
55
Two related publications have dealt with the so-called molecular motors (2).
The unidirectional motion observed with such molecules occurs on exposure to
visible light.13,14 A further example (3) of a chiroptical switch has been
synthesized and studied. The isomerization of the (3S,3 0 S)-trans derivative
(3) affords a mixture of the cis and trans isomers.15
1.1.1 Stilbene and Related compounds. As a result of calculations on the

isomerization of ethene, it has been suggested16 that ‘there is a need for the
reconsideration and refinement of the photoisomerization mechanism of stil-
bene’. Both a semi-classical approach17 and simulations18 have been employed
to study the cis,trans-isomerization of stilbene. Simulations have examined the
photoisomerization of stilbene, and ab initio quantum chemistry has also been
utilized to study this system.19
Donor-acceptor stilbene systems with N,N-dimethylamino groups as the
donor and pyridine, thiophene, quinoline and other aryl groups as acceptors
exhibit electrogenerated chemiluminscence by intramolecular charge transfer.20
The influence of N-substituents (methyl and phenyl) on the photophysical
behaviour of trans-4-aminostilbene has been evaluated.21 Calculations have
been carried out on trans-4-dimethylamino-4 0 -cyanostilbene, and the torsion
within the central ethenic moiety was calculated. The isomerization of such
systems was discussed.22
Liu and co-workers23 have shown that irradiation of the 2,2 0 -dimethyl-
stilbene isomers in glassy 2-methylpentane brings about isomerization by a
hula-twist mechanism. A hula-twist mechanism to afford the trans isomer is
also involved in the isomerization of a complex (1 : 1) of cis-3,3 0 -bis(di-
phenylhydroxymethyl)stilbene and acetone.24 The conformational dynamics
of stilbenes such as (4) within dendrimers have been studied.25 Lewis et al.26
have reported the use of the stilbene derivative (5) as the linker in DNA
hairpins. The photochemical isomerization of resveratrol27 (3,5,4 0 -trans-
trihydroxystilbene) and trans-3,3 0 ,5,5 0 -tetramethoxystilbene has been exam-
ined. Photocyclization of the cis isomer of the latter stilbene to a phenanthrene
occurs readily.28 Cyanoaromatics have been used as sensitizers for the one-way
isomerization of 1,1-diaryl-2-t-butylethene.29
The (Z)-stilbene (6) does not form a rotaxane with dibenzo-24-crown-8 but,
when the stilbene is isomerized (sensitized by benzil) to the E form, a pseudo-
rotaxane is formed.30 Lewis and Crompton have reported that the photoacidity
of the stilbene derivatives (7) and (8) is dependent on the position of the
hydroxy group on the stilbene, and as a consequence the meta derivative
undergoes isomerism.31 The influence of the nitrogen atoms on the photo-
chemistry of the 1,4-distyrylbenzene analogue (9) and related compounds has
been assessed.32 The photophysics and conformational analysis of the stilbene
dimer (10) have been studied.33 Modelling of the optical properties of the
stilbenophane (11) has been reported.34
1.1.2 The Dithienylethene System and Related Compounds. The area of diaryl-
ethenes has been the subject of a review.35 Calculations have been carried out
dealing with the photochromism of such compounds.36 A description of the
preparation of diarylethene nanoparticles has been published, and a decrease in
photocyclization was attributed to aggregation.37 Some novel photochromic
diarylethenes have been synthesized. The photochemistry exhibited by these
compounds suggests that they could be of use as optical switches.38 Tian and
Yang39 have reviewed the area of diarylethene photochromic switches. 1,2-
Bis(2-methylbenzo[b]thiophen-3-yl)hexafluorocyclopentene is at the basis of a
new photochromic liquid crystal system.40 Yokoyama and his co-workers have
patented details for such photochromic materials.41
Single crystals composed of the three diarylethenes (12)–(14) have been
demonstrated to undergo a variety of colour changes dependent upon the
wavelength used.42 Other studies have also investigated photochromism
within the crystals of diarylethenes.43 The presence of the alkynyl substituents
in the diarylethenes (15) has been shown to enhance the cycloreversion of the
derivatives,44 and some new photochromes have been synthesized by
Kobatake and Irie,45 in an examination of the influence of alkyl groups at
the reacting carbons and also the effect of extended conjugation to
heteroatoms. The irradiation of (16) at 350 nm brings about the usual

cyclization to yield a coloured product. The influence of the changes can be
seen in the data recorded under the structure.45 Interesting new systems have
been developed based on the cyclization of the bisthienylalkene (17) to the
closed form (18).46 The latter was then converted chemically into the
cyclophane (19), which underwent ring opening to yield the open form (20).
The quantum yield for the cyclization of (20) to (19) was 0.67. Interestingly,
the closed form (19) is thermally stable up to 1001C. The absolute asymmetric
photocyclization of the diarylethene derivatives (21) and (22) has also been
described. The compounds (21) and (22) do not interchange on irradiation.
Thus, in the crystal, (21) is converted to the R,R closed form while (22) gives
the S,S form.46 The chiral diarylethene (23) undergoes diastereoselective
cyclization on irradiation in the crystal.47 The influence on photochromism
of hydrogen bonding in the related carboxylic acid derivatives (24) has been
detailed.48
The two pentafluoroaryl derivatives (25) form a 1 : 1 co-crystal of alternate

layers of the different molecules. Reversible colour changes were observed on
irradiation.49 Kobatake and Irie50 have described the photochemical reactivity
of the dimeric system (26). Irradiation at 313 nm brings about purple blue
colouration of the hexane solution of (26). Continued irradiation changes the
colour to blue. The colour changes are due to the formation of compounds with
one closed form and two closed forms. The dimer (27) undergoes a single ring
closure on irradiation at 350 nm in hexane solution.51 Two cyclization modes
are also described for the irradiation of (28).52
The dynamics for the ring opening of the diarylethene derivative (29) has
been shown53 to be a one-step process with a reaction rate of 1.7 1010 s1.
Reversible changes in the optical rotation have been observed on irradiation of
(30) in stretched DNA-quaternary ammonium ion complex films.53 The influ-
ence of cyano substituents has also been quantified for the derivative (31).
Apparently, the cycloreversion quantum yield for the closed form of (31) is 30
times larger than for alkyl substituted derivatives.54 Other factors can control
the quantum yield of cyclization and, for the cyclization of 1,2-bis-(2-methyl-5-
phenyl-3-thienyl)perfluorocyclopentene, when compared that of 1,2-bis-(2-
methyl-1-benzothiophen-3-yl) perfluorocyclopentene in the crystalline phase,
the initial geometries of the alkenes are important.55 Irradiation of the racemic
bisthienylethene (32a) at 313 nm in hexane affords two diastereoisomeric
cyclized products. The de was established as 87%. The closed compounds
return to the open form on irradiation at 510 nm.56 Yokoyama and co-
workers57 have studied the photochromism of the derivative (32b) in a DNA-
quaternary ammonium ion complex film. Under these conditions, however, no
photochromism was observed owing to the ethene (32b) being in the wrong
conformation. Yagi and Irie58 have reported the photochromic behaviour of
indole derivatives (33) based on the usual hexafluoroethene moiety. Irradiation
at 366 nm converts the open form to a coloured closed form, which can be ring-
opened using wavelengths 4480 nm. The derivative (34) is also photochromic
and affords a highly thermally stable closed ring form.59
Interest in photochromic systems other than those based on the hexa-

fluorocyclopentene moiety continues to grow. The photochemical reactivity
of the two photoswitches (35) is similar, and irradiation is efficient with
conversions of 85% and quantum yields of around 0.6.60 The novel photo-
chromic systems (36) undergo reversible ring closure in a reaction analogous to
that observed in the bisthienyl system.61 Qin et al.62 have studied the novel
pyridyl substituted cyclopentene system (37). This undergoes photocyclization
with an enhanced quantum yield when the reactions are carried out in the
presence of a metal. The pyridine units are capable of co-ordinating with the
metal. The photochromic dithienylethene unit tethered to b-cyclodextrin (38)
has been used as a photoswitch to control the uptake of porphyrin.63 A series of
new photochromic molecules (39) have been synthesized and studied. These
exhibit the usual cyclization on irradiation.64 The terthiophene derivatives (40)
exhibit reversible photochemical cyclization (at 313 nm) and reversion (at
wavelengths 4460 nm) reactions. The cycles can be carried out many times
without apparent degradation.65 A novel bisthienylethene photochrome (41)

has been synthesized and studied. The compound, in a polymer film, undergoes
ring closure on irradiation at 254 nm and the product ring opens at 450 nm.66
1.2 Miscellaneous Reactions. – Miranda and his co-workers67 have investi-

gated the formation of o-quinone methides by the photochemical reactions of
the phenol derivatives (42). Excitation of these brings about proton transfer to
afford the zwitterions (43), which then undergo ring opening of the cycloalkyl
moiety to afford the quinone methides. There is a ring-size effect, and the best
results are obtained using the cyclohexenyl derivatives. The authors69 also
observed that the presence of the CF3 group accelerated the formation of the
methide, whereas the MeO group slowed down the reaction. Both 1,2,4-
triphenylbenzene and the binaphthalene derivative (44) sensitize the aminations
illustrated in Scheme 1. The reactions involve electron transfer, and produce
radical cations as the key intermediates. Apparently, a key step is the hole
transfer from the radical cations to the sensitizer.68
Wan and his co-workers69 have reported the photohydration and photo-
solvolysis of the alkenes (45). The reactions involve the intermediacy of quinone-
methide type intermediates. Flash photolysis of coniferyl alcohol (46) and
isoeugenol (47) in acetonitrile has supplied evidence for the formation of the
corresponding radical cations. These transient species react readily with water
and other hydroxylic solvents to afford 4-vinylphenoxyl radicals.70
Scheme 1
The vacuum-UV photodissociation of ethene has provided evidence for the

formation of CH fragments.71 Eleven photofragments have been detected
following the photodissociation of propene, where the principal reaction
channel followed is the formation of ethyne, methyl radicals and hydrogen
atoms.72 The elimination of HCl from vinyl chloride has been studied using
irradiation at 193 nm, and a concerted mechanism is suggested from the results
obtained.73 Vinyl bromide undergoes conversion to the vinyl radical on irra-
diation at 193 nm using an excimer laser.74 A detailed study has examined the
mechanism for the formation of a primary vinyl cation from the styrene (48).75
The influence of substitution on the alkenes (49) has been assessed. The study
has shown that styrenes with o-methyl and a-methyl groups adopt orthogonal
geometry. This results in a blue shift in the pp* transition.76 The ocimene
derivative (50) is formed on irradiation of the pinene derivative (51). There is no
evidence for [2 þ 2]-cycloaddition, and the rearrangement occurs on irradiation
in benzene or methanol. Excitation results in triplet energy transfer from the
benzene moiety to the pinene. The ring opening affords the cis isomer (50), but
continued irradiation affords a ratio, trans:cis, of 52 : 48.77
1.2.1 Addition Reactions. A patent has described a method for the formation
of perfluoroalkyl iodides. This consists of irradiating (254 nm) a mixture of
perfluoroethyl iodide with tetrafluoroethene at elevated temperatures and
pressures.78
Methanol addition results on irradiation of 2,3-dimethylbut-2-ene in a
mixture of 1,4-dicyanobenzene and phenanthrene in the presence of acrylo-
nitrile or methyl acrylate.79 Inoue and co-workers80 have studied the enantio-
differentiating addition of alcohols to the 1,1-diphenylethene derivatives (52).
The reactions are sensitized by the naphthalenecarboxylates (53) and (54),
where the R* groups are saccharide moieties. The ee of the products (55) is
influenced by steric, electronic and solvent effects. Efficient addition of water to
3-hydroxystilbene can be brought about on irradiation in acetonitrile-water
mixtures.81 Pincock has highlighted the importance of the discovery in 1973 of
the formation of the radical cation of 1,1-diphenylethene.82 Grainger and
Patel83 have described a new photochemical approach to cuparene (56). The
reaction involves the electron-transfer induced cyclization of the styrene
derivative (57), which affords the two cycloadducts (58) and (59) in a ratio of
6 : 1. The major isomer (58) was converted to racemic cuparene. The incorpo-
ration of an optically active amine affords the styrene (60). This also undergoes
photochemical cyclization on irradiation at 265 nm in hexane. Four diastereo-
isomers are obtained and one of the major products is (61), which can be
converted to (–)-cuparene.
1.2.2 Reactions of Alkynes. Propyne undergoes fission on irradiation at 193

d
nm. This treatment affords the propargyl radical (CH2CCH) and ethyne.
Irradiation (at wavelengths 4120 nm) of cyanoacetylene in a matrix at 10 K
gives evidence for the formation of three different isomers.84 A C2HO radical is
formed on irradiation (at 193.3 nm) of ethyl ethynyl ether. This fragmentation
path amounts to 37% of the overall processes.85 The propargyl radical is
formed on irradiation of propargyl chloride at 193 nm or propargyl bromide at
248 nm.86,87 Others88 have also investigated this process. Vinyl cations can be
formed by flash irradiation of the alkynes (62).89 Hydrosilylation of alkynes has
been achieved using irradiation at 350 nm in the presence of a Pt(II) catalyst.90
A silacyclopropene intermediate is involved in the photochemical cyclization of

1-(3-hydroxy-2-pyridyl)-2-(pentamethyldisilanyl)ethyne.91,92
The Bergman cyclization of the copper complex (63) or its zinc counterpart
involves the triplet state of the enediyne. The cyclization affords the derivative
(64).93 Irradiation of the diethynylsulfides (65) at 300 nm in the presence of a
hydrogen donating additive (cyclohexadiene or alcohols) results in cyclization.
This reaction is of the photo-Bergman type and affords modest yields of 3,4-
subsituted furans. The diphenyl-substituted product (66) is obtained in 16%
yield and is accompanied by phenylacetylene as a by-product.94 Irradiation (at
254 nm in n-hexane) of the cyclodecatriene derivatives (67) results in cheletropic
extrusion of the bridge as a carbene. This rearranges into the triynes (68)
obtained in the yields shown. An additional reaction process is rearrangement
of the skeleton of (67) to afford the products (69).95 The photon-absorption
properties of the macrocycles (70) have been measured.96
2 Reactions Involving Cyclopropane Rings
2.1 The Di-p-Methane Rearrangement and Related Processes. – Armesto and

co-workers97 have reviewed recent advances in di-p-methane photochemistry.
Scheffer and Vishnumurthy98 have described the photoconversion of the enone
(71) into the cyclopropane derivative (72). This occurs by a 1,2-phenyl migra-
tion in an example of a di-p-methane rearrangement. The reaction is very
efficient, and the authors100 speculate that steric acceleration of the migration
of phenyl from the triphenylmethyl group occurs. The photochemical reactivity
of compounds related to 1,1-dicyano-3-phenylpropene has been studied. This
work was aimed at comparing the di-p-methane reactivity with cyclization
involving hydrogen migration and bond formation. Apparently, electron
donating groups on the aryl ring and polar solvents decrease the di-p-methane
pathway but have little or no effect on the other cyclization mode.99
A study of the di-p-methane reactivity of the barrelene derivatives (73) in

zeolites has been published. The reaction in a slurry affords a 77 : 23 mixture of
(74) and (75); when the reaction is carried out in a zeolite the cyclooctatetraene
product is suppressed and the two products are obtained in a ratio of 1 : 99.
This enhancement of the di-p-methane reactivity occurs with Li1- and Na1-
exchanged zeolites.100 Liao and co-workers101 have reported new reactivity of
some barrelenes. The reactions encountered are sensitive to substitution
pattern. Thus, the irradiation of (76) with electron withdrawing groups follows
the di-p-methane route, to yield (77) and (78) predominantly. The less heavily
substituted derivative (79) behaves differently, and irradiation affords (80) and
(81) by the aza-di-p-methane rearrangement, with (82) formed only in small
amounts by the alternative di-p-methane path. Calculations have been used to
examine the mechanism of the barrelene-semibullvalene isomerization. These
results indicate that two biradical intermediates are involved in the T1 state.102
Other calculations on the di-p-methane rearrangement of barrelene substanti-
ate the Zimmerman mechanism for the sensitized rearrangement.103
Zimmerman and Novak have continued the search for further examples of
the tri-p-methane process. Some of the systems studied are illustrated by (83).
Sensitized irradiation of these compounds brings about the di-p-methane
reaction affording (84) and (85). The tri-p-product (86) is not formed under
sensitized conditions, and direct irradiation is needed to produce this product.
A secondary product (87) is also formed. The regioselectivity of the process was
studied in detail.104
Armesto and his co-workers105 have reported further on their interesting new
reactions of azadienes. Acetophenone-sensitized reactions of the imines
(88)–(92) results in the formation of a variety of products. These, with yields,
are shown in Scheme 2.
2.2 Miscellaneous Reactions Involving Three-Membered Ring Compounds. –

Asymmetric induction within 1,2-diphenylcyclopropane on photolysis in
b-cyclodextrin has been studied.106 Recent research has shown that cis-2,3-
diphenylcyclopropane-1-carboxylic acid does not undergo ISC on direct
irradiation. The reaction encountered is isomerization to the corresponding
trans isomer via a 1,3-biradical intermediate.107 Exothermic bond cleavage is
the dominant reaction within radical cations of cyclopropylamines formed by
SET to DCA.108 The photoheterolysis of 9-cyclopropyl-9-fluorenol has been
studied in non-acidic zeolites. The rate of formation of the resultant cation is
dependent upon the alkali metal counterion.109
A detailed spectroscopic and calorimetric study of the photorearrangements
of (93) has shown that both zwitterionic and biradical species are involved in
the isomerization.110 DCA-sensitized irradiation of the bicyclopropenyl com-
pounds (94) results in conversion into Dewar benzene derivatives (95) and (96)
and eventually into the corresponding benzene derivatives (97). The irradiation
Scheme 2
of (94, R ¼ Me) affords the three products (95), (96) and (97) in ratios of
24 : 16 : 46, and prolonged irradiation gives (95) and (97) in a ratio of 28 : 72.
Compound (94, R ¼ H) affords the three products in ratios of 18 : 41 : 35.111
Laser irradiation at 266 nm of the cyclopropylbutene system (98, R ¼ H or

CO2Et) results in the formation of the radical by C–Se bond fission. This
radical cyclizes to afford (99a,b), which ultimately undergoes cyclization to
(100). This study was aimed at proving the mechanism of the a-methylene-
glutarate-mutase-induced rearrangement of 2-methyleneglutarate to 3-methy-
litaconate.112
The two-bond photochemical cleavage product, 1,5-hexadiene, obtained from

bicyclo[3.1.0]hexane arises from the first excited singlet state of the starting
material. This proposal has been substantiated by calculations at the CASSCF
level.113 Both cis- and trans-9-diphenylvinylidene-bicyclo[6.1.0]nonanes undergo
isomerization on irradiation in the presence of Michler’s ketone.114
3 Reactions of Dienes and Trienes
Irradiation of the cyclobutene derivatives (101) at either 214 nm or 228 nm

affords mixtures of dienes with a greater preponderance of the product arising
from disrotatory ring opening. The authors115 suggest that these results indi-
cate that Rydberg-derived ring opening is dependent upon the ability of the
molecules to twist around the central bond as ring opening occurs.
Reviews of the hula-twist photoisomerization of dienes have been pub-

lished.116,117 New calculations dealing with the isomerism of s-cis-butadiene
have been reported.118 Molecular dynamic simulations of the photochemical
behaviour of butadiene have shown that cis-trans isomerism occurs.119,120 The
regioselectivity observed in the photochemical isomerism of trans,trans-1-
fluorohexa-2,4-diene is proposed as due to electrostatic control.121 Direct
irradiation of the fluorinated dienes (102) results in preferential conversion to
the 1Z,3E isomers (103).122 DCA-sensitized irradiation of the butatrienes
(104) in various alcohols afford the adducts (105). The simpler alcohols give
moderate yields of product, while t-butanol affords only a trace of the
adduct.123
Miyazaki and Yamada124 report that irradiation of cyclopentadiene in an

argon matrix with a super-high-pressure Hg lamp results in the formation of
bicyclo[2.1.0]pent-2-ene. By irradiation at shorter wavelengths the initial prod-
uct is transformed into allylacetylene and vinylallene. The photochemical ring
opening of the cyclohexadiene moiety within the triterpenoids (106) yields the
corresponding trienes.125 The tricyclo[4.3.1.0]dienes (107) have been used as a
source of some fluorocarbenes: irradiation affords the carbenes with indane
produced as the by-product.126
The divinyl benzene molecule (108) is reported to undergo intramolecular

addition to yield an exo-endo mixture of (109) in 10% yield. Other products
such as phenanthrenes are also formed.127 Saltiel et al.128 have reported a study
of the photoisomerizsationof all-trans-1,6-diphenylhexa-1,3,5-triene in aceto-
nitrile. Their observations show that the isomerization is mainly via the singlet
excited state, since there is low intersystem crossing within this triene. Inter-
estingly, the presence of oxygen enhances terminal bond isomerization. The
mechanism for the interaction is thought to involve a charge transfer between
the triene and oxygen, leading to either a zwitterion or a biradicaloid inter-
mediate. Irradiation of the cycloheptatriene (110) brings about two processes
identified as photoheterolysis and hydrogen migration. The first process results
from loss of methoxide and affords the corresponding tropylium methoxide,
while a 1,7-hydrogen migration occurs in competition, with the exclusive
formation of 5-(4-dimethylaminophenyl)-1-methoxycyclohepta-1,3,5-triene.129
The photochemical isomerization of trans-vitamin D3 to the cis isomer has

been achieved under conditions where the vitamin was tethered to a silica gel
substrate.130 A continuous photoreactor has been described for the photo-
chemical conversion of ergosterol into vitamin D2.131 Saltiel et al.132 have
studied the isomerization within the 25-hydroxytachysterol and the 25-
hydroxyprevitamin D3 systems shown in Scheme 3. The study used a two-
stage irradiation at 254nm to 313 nm, and this results in conformer-specific
photoconversion.
Scheme 3
4 (2p þ 2p)-Intramolecular Additions
The complex of (111) with copper triflate undergoes photochemical conversion

into the adduct (112). The yields are high for this process. A similar cyclization
can be carried out with (113). When the bis-dienes (114) are used, cyclization
affords the adducts (115). These cyclizations provide new routes to
bicyclo[3.2.0]heptanes and bicyclo[6.3.0]undecanes.133
The donor acceptor norbornadiene derivative (116) exhibits high quantum

yields for valence isomerization using blue light.134 Intramolecular electron
transfer is involved in ring opening of the quadricyclane derivative (117) to
the corresponding norbornadiene. The study has indicated that electron trans-
fer occurs from the quadricyclane moiety to the BF2 chromophore.135 Further
work on such systems has shown that intramolecular triplet energy transfer
from the carbazole to the norbornadiene moiety also occurs in the molecule
(118).136
Nishimura et al.137 have described a path to crownopaddlanes by the

(2 þ 2)-intramolecular cycloadditions of the compound (119). The sensitivity
of the resultant compounds towards ions was assessed. The new crown-
ophanes (120, n ¼ 2-4) have been synthesized by irradiation of the corres-
ponding divinyl derivatives.138 The vinylpyridine derivatives (121) are also
reactive, and afford the (2 þ 2)-adduct (122) in yields that can be as high as
84% (n ¼ 4 and 8).139 Nishimura and his co-workers have reviewed this area
of research.140
5 Dimerization and Intermolecular Additions
Calculations have studied the (2 þ 2)-photocycloaddition of ethene, either

under direct conditions141 or on a Si (100) surface.142
Inokuma et al.143 have reported a further example of additions with crown
ether derivatives. In this instance the additions are intermolecular and involve the
dimerization of the vinylbenzene derivative (123) to afford the two adducts (124)
and (125). The ion-complexing capabilities of the adducts were assessed. A
layered ternary solid is formed between 1,2-dihydroxybenzene and trans-1-(2-
pyridyl)-2-(4-pyridyl)ethylene. Within this, the stilbene is held in a head-to-tail
arrangement. Irradiation brings about the formation of a cyclobutane identified
as (R)-cis,trans,trans-1,3-bis(2-pyridyl)-2,4-bis(4-pyridyl)cyclobutane.144 An ex-
tension of this work to the use of 5-methoxyresorcinol as the template has
demonstrated that quantitative yields of ladderanes (126) can be obtained by
irradiation of the solid-state units represented as (127).145 The diazastilbene
derivative (128) readily forms complexes with the tetra-acid (129). This acts as a
supramolecular template and holds the ethene systems close enough for photo-
chemical dimerization.146
The styrylpyrilium salt derivatives (130) undergo (2 þ 2)-cycloaddition to

afford the corresponding dimers. The magnetic properties of the radical cations
formed from these dimers were compared with those formed from (130).147
Styryl dyes of the type shown as (131) undergo E-Z isomerization on irradi-
ation at 436 nm. The dyes align themselves in the pattern shown in (132, where
the filled blob represents the crown ether complex). These undergo dimerization
on irradiation to afford compounds (133), from which the magnesium ions can
be removed.148
Cross-photodimerization of (E)-2-(2-phenylethenyl)benzoxazole and (E)-4-

[2-(4-chlorophenyl)ethenyl]-pyridine in sulfuric acid solution results in the
formation of a product identified as (R)-cis,trans,trans-1-(2-benzoxazolyl)-2-
(4-chlorophenyl)-4-phenyl-3-(4-pyridinyl)cyclobutane.149,150
Nishimura and his co-workers151 have reported the synthesis of the calixa-
rane derivatives (134). These are formed by photoaddition of ethene to the
corresponding alkene derivative.
Photodimerization of acenaphthylene in cation-exchanged bentonite clays

has shown that the cis dimer (135) is formed preferentially with smaller cations.
Heavier ions favour the formation of (136).152
6 Miscellaneous Reactions
6.1 Reactions of Halo Compounds. – Di-(p-methoxyphenyl)methyl chloride

undergoes a variety of processes when irradiated with a three-laser system at
308 nm, 355 nm and 495 nm. This treatment leads to the formation of the
ground-state radical, an excited state radical and the corresponding cation.
Irradiation at 308 nm brings about the fission of the C–Cl bond, while 355 nm
raises this radical to its excited state and also affords the cation.153 The benzyl
chloride derivatives (137) undergo photolysis in aqueous acetonitrile to yield
the corresponding benzyl alcohol and the reduction product 4-
RC6H4C(CF3)H.154
The photobehaviour of methyl iodide clusters is dependent on the mode of

excitation. Thus, in a supersonic jet iodine molecules are formed,155 while a
visible laser forms ions.156 Pulsed photolysis has been used to generate iodine
atoms from trifluoromethyl iodide.157
The allyl-d2 radical is formed on irradiation of allyl-d2 iodide at 193 nm.158
Allyl radicals are also formed by irradiation of allyl alcohol at the same
wavelength. The dissociation in this instance occurs to form a triplet state
following pp* excitation.159
The results obtained from the irradiation at 235 nm of vibrationally excited
dichloromethane suggest that there is higher non-adiabaticity for vibrationally
excited molecules.160 Laser irradiation at 355 nm of methylene chloride and
methylene bromide brings about ionization.161 A simple C–Br bond fission is
the key step in the photodissociation of methylene dibromide at 248 nm.162
Ionization of methylene bromide in the 10–24 eV range has been reported.163
Irradiation of methylene iodide in water has provided evidence for the forma-
tion of iodine atoms and protons.164 Further work on the photochemical
behaviour of methylene iodide has reported that vibrationally relaxed CH2I I
reacts with cyclohexene to afford norcarane.165
The photodissociation of bromoform at 193 nm has been studied using
dispersed fluorescence.166 Bromoform also undergoes fission on irradiation at
234 and 267 nm.167 A series of n-alkylbromides has also been studied on
irradiation at the same wavelengths.168 Prompt C–Br bond fission occurs on
irradiation of bromoform at 248 nm.169 The isomerization of bromoform
into isobromoform occurs on irradiation in water. Insertion of OH into
isobromoform results in the formation of the final products, HBr, CO and
formic acid.170
Bromine atoms are formed on irradiation of difluorobromochloro-

methane at 267 nm.171 Photodissociation of trifluoroiodomethane at 248
nm has been studied using a high-resolution photofragment translational
spectrometer.172
Chen et al.173 have reported the use of irradiation of CBr4 in methanol as a
selective reagent for the removal of protecting groups. Many examples were
given, but two will suffice to illustrate what can be achieved. Thus, the
conversion of (138a) into (138b, 89%) can be brought about by irradia-
tion for 24 h. A more facile reaction is the conversion of (139a) into (139b,
86%) in 6 h.
The photodissociation of 1-bromo-2-chloroethane at 193 nm demonstrated

that there were no stable bromoethyl or chloroethyl radicals formed. Dissoci-
ation of these radicals is rapid and affords ethene.174 1-Chloro-1,1,3,3,3-
pentafluoropropane can be made regioselectively by the photochlorination of
1,1,1,3,3-pentafluoropentane.175
Irradiation of 2-iodooctane in methanol at 254 nm results in the formation of
many products. The ones containing oxygen arise from the 2-octyl carbocation.
Laser irradiation at 266 nm of the same compound in methanol affords only
three products, octane and alkenes are formed. The authors176 suggest that
excitation produces a short-lived ns* excited state, which dissociates into a
radical pair; and it is from this that the products are formed. Sun et al.177 report
that carbonylation of alkyl halides can be brought about using CO and suitable
catalysts. Harato et al.178 have also reported the carbonylation of alkyl chlo-
rides using SmI2 as a catalyst and CO at 50 atm. These authors consider that an
acyl samarium species might be involved in the reaction. Cobalt acac catalysis
has been used to carboxylate alkenes at ambient conditions.179 The use of
InCl3-MgCO3-Co(acac)2 in methanol-acetone mixtures gives improved yields
of methoxycarbonylated alkanes from halocycloalkanes. Some of the results
are shown in Scheme 4.
Scheme 4
6.2 Miscellaneous Rearrangements and Bond Fission Processes. – Methacrylo-

nitrile undergoes C–CN bond fission on irradiation at 193 nm.180 Substitution
of the bromo group by the anion of nitromethane occurs when 1-bromo-,
2-bromo-, 1,3-dibromo- and 1,4-dibromoadamantane are irradiated in DMSO-
ammonia solution.181 Photodissociation of jet-cooled propan-1-ol and propan-
2-ol at 193.3 nm shows that O–H bond fission is the dominant reaction.182
Albini and his co-workers have described the generation of alkyl radicals from
cyclopentane, cyclohexane and cyloheptane. This reaction is carried out by
irradiation in the presence of tetrabutylammonium decatungstate. The resul-
tant radicals can be trapped efficiently (63%) by electrophilic alkenes such as
acrylonitrile.183 Zwitterionic intermediates are generated by O–C bond fission
on irradiation of the pinacols (140) in methanol solution.184
References
1. (a) C.M. Gordon, NATO Sci. Ser., II, Math. Phys. Chem., 2003, 92, 365;
(b) C.M. Gordon, Chem. Abstr., 2003, 139, 92605.
2. P.H. Dürr and H. Bouas-Laurent (ed.), Photochromism, revised edn., Elsevier,
Amsterdam, 2003.
3. (a) M.J. Oelgemoller and Y. Inoue, J. Photosci., 2003, 10, 71; (b) M.J. Oelgemoller
and Y. Inoue, Chem. Abstr., 2003, 139, 84817.
4. (a) Y. Inoue, Sentan Kagaku Shirizu, 2003, 2, 93; (b) Y. Inoue, Chem. Abstr., 2003,
139, 330167.
5. (a) C.-j. You, R. Xie, G.-q. Yang and Y. Li, Gangguang Kexue Yu Guang Huaxue,
2003, 21, 147; (b) C.-j. You, R. Xie, G.-q. Yang and Y. Li, Chem. Abstr., 2003, 139,
84809.
6. H.-B. Yi, X.-H. Duan, J.Y. Lee, H.M. Lee, X.-Y. Li and K.S. Kim, J. Chem. Phys.,
2003, 119, 8854.
7. A. Viel, R.P. Krawczyk, U. Manthe and W. Domcke, Angew. Chem. Int. Edn.,
2003, 42, 3434.
8. G. Krishnamoorthy, A.E. Asato and R.S.H. Liu, J. Chem. Soc., Chem. Commun.,
2003, 2170.
9. (a) F.D. Lewis and X. Zuo, Spectrum, 2003, 16, 8; (b) F.D. Lewis and X. Zuo,
Chem. Abstr., 2003, 139, 381011.
10. (a) F.D. Lewis and X. Zuo, Photochem. Photobiol. Sci., 2003, 2, 1059; (b) F.D. Lewis
and X. Zuo, Chem. Abstr., 2004, 140, 303178.
11. (a) M.J.R. Reddy, V.V. Reddy, U. Srinivas, M.J.R. Reddy and V.J. Rao, Proc. Ind.
Acad. Sci., Chem. Sci., 2002, 114, 603; (b) M.J.R. Reddy, V.V. Reddy, U. Srinivas,
M.J.R. Reddy and V.J. Rao, Chem. Abstr., 2003, 139, 21843.
12. (a) J. Saltiel, G. Krishnamoorthy and D.F. Sears Jr., Photochem. Photobiol. Sci.,
2003, 2, 1162; (b) J. Saltiel, G. Krishnamoorthy and D.F. Sears Jr., Chem. Abstr.,
2004, 140, 225621.
13. R.A. van Delden, N. Koumura, A. Schoevaars, A. Meetsma and B.L. Feringa,
Org. Biomol. Chem., 2003, 1, 33.
14. R.A. van Delden, J.H. Hurenkamp and B.L. Feringa, Chem.-Eur. J., 2003, 9, 2845.
15. R.A. van Delden, M.J.K. ter Wiel and B.L. Feringa, J. Chem. Soc., Chem.
Commun., 2004, 200.
16. J. Quenneville and T.J. Martinez, J. Phys. Chem. A., 2003, 107, 829.
17. Y. Dou and R.E. Allen, J. Chem. Phys., 2003, 119, 10658.
18. Y. Dou and R.E. Allen, Chem. Phys. Lett., 2003, 378, 323.
19. D.M. Letiner, B. Levine, J. Quenneville, T.J. Martinez and P.G. Wolynes, J. Phys.
Chem. A., 2003, 107, 10706.
20. (a) C.-Y. Chen, J.-H. Ho, S.-L. Wang and T.-I. Ho, Photochem. Photobiol. Sci.,
2003, 2, 1232; (b) C.-Y. Chen, J.-H. Ho, S.-L. Wang and T.-I. Ho, Chem. Abstr.,
2004, 140, 225613.
21. (a) J.-S. Yang, C.-M. Wang, C.-Y. Hwang, K.-L. Liau and S.-Y. Chiou, Photochem.
Photobiol. Sci., 2003, 2, 1225; (b) J.-S. Yang, C.-M. Wang, C.-Y. Hwang, K.-L. Liau
and S.-Y. Chiou, Chem. Abstr., 2004, 140, 303233.
22. (a) Y. Amatatsu, Chem. Phys. Lett., 2003, 369, 673; (b) Y. Amatatsu, Chem. Abstr.,
2003, 138, 346339.
23. Y. Imamoto, T. Kuroda, K. Takayuki, S. Shevyakov, G. Krishnamoorthy and
R.S.H. Liu, Angew. Chem. Int. Edn., 2003, 42, 3630.
24. K. Tanaka, T. Hiratsuka, S. Ohba, M.R. Naimi-jamal and G. Kaupp, J. Phys.
Org. Chem., 2003, 16, 905.
25. H. Tatewaki, T. Mizutani, J. Hayakawa, T. Arai and M. Terazima, J. Phys. Chem.
A., 2003, 107, 6515.
26. M. Egli, V. Tereshko, G.N. Mushudov, R. Sanishvili, X.Y. Liu and F.D. Lewis,
J. Am. Chem. Soc., 2003, 125, 10842.
27. (a) M. Deak and H. Falk, Monatsh. Chem., 2003, 134, 883; (b) M. Deak and H. Falk,
Chem. Abstr., 2004, 140, 59433.
28. A. Momotake, M. Uda and T. Arai, J. Photochem. Photobiol. A: Chem., 2003
158, 7.
29. (a) Y. Kawamura, T. Ishiduka and M. Tsukayama, Int. J. Modern Phys. B: Condensed
Matter Phys., Statistical Phys. Appl. Phys., 2003, 17, 1492; (b) Y. Kawamura,
T. Ishiduka and M. Tsukayama, Chem. Abstr., 2003, 139, 213988.
30. Y. Tokunaga, K. Akasaka, K. Hisada, Y. Shimomuraa and S. Kakuchi, J. Chem.
Soc., Chem. Commun., 2003, 2250.
31. F.D. Lewis and E.M. Crompton, J. Am. Chem. Soc., 2003, 125, 4044.
32. E. Marri, D. Pannacci, G. Galiazzo, U. Mazzocato and A. Spalletti, J. Phys. Chem.
A., 2003, 107, 11231.
33. A. Ruseckas, E.B. Namdas, J.Y. Lee, S. Mukamel, S.J. Wang, G.C. Bazan and
V. Sundstrom, J. Phys. Chem. A., 2003, 107, 8029.
34. J. Gierschner, H.G. Mack, D. Oelrug, I. Waldner and H. Rau, J. Phys. Chem. A.,
2004, 108, 257.
35. (a) V.F. Razumov and M.V. Alfimov, Zhur. Nauch. Prokly. Fotografii, 2003, 48,
28; (b) V.F. Razumov and M.V. Alfimov, Chem. Abstr., 2004, 140, 329371.
36. M. Boggio-Pasqua, M. Ravaglia, M.J. Bearpark, M. Garavelli and M.A. Robb,

J. Phys. Chem. A., 2003, 107, 11139.
37. F. Sun, F. Zhang, F. Zhao, X. Zhou and S. Pu, Chem. Phys. Lett., 2003, 380, 206.
38. X. Zhou, F. Zhang, H. Guo, P. Sun, S. Pu and P. Yuan, Proc. SPIE- Int. Soc. Opt.
Engineer., 2003, 5060, 48.
39. H. Tian and S. Yang, Chem. Soc. Rev., 2004, 33, 85.
40. (a) M. Frigoli and G.H. Mehl, ChemPhysChem., 2003, 4, 101; (b) M. Frigoli and
G.H. Mehl, Chem. Abstr., 2003, 138, 328160.
41. (a) T. Sato, T. Kosaka, Y. Yokoyama and T. Okuyama, Jpn. Kokai Tokkyo Koho,
JP, 2003, 321, 467; (b) T. Sato, T. Kosaka, Y. Yokoyama and T. Okuyama, Chem.
Abstr., 2003, 139, 388553.
42. M. Morimoto, S. Kobatake and M. Irie, J. Am. Chem. Soc., 2003, 125, 11080.
43. S. Kobatake and M. Irie, Bull. Chem. Soc. Jpn., 2004, 77, 195.
44. K. Morimitsu, S. Kobatake and M. Irie, Tetrahedron Lett., 2004, 45, 1155.
45. S. Kobatake and M. Irie, Chem. Lett., 2003, 1078.
46. S. Yamamoto, K. Matsuda and M. Irie, Angew. Chem. Int. Edn., 2003, 42, 1636.
47. S. Yamamoto, K. Matsuda and M. Irie, Org. Lett., 2003, 5, 1769.
48. S. Yamamoto, K. Matsuda and M. Irie, Chem.-Eur. J., 2003, 9, 4878.
49. (a) M. Morimoto, S. Kobatake and M. Irie, Photochem. Photobiol. Sci., 2003, 2,
1088; (b) M. Morimoto, S. Kobatake and M. Irie, Chem. Abstr., 2004, 140, 243430.
50. S. Kobatake and M. Irie, Tetrahedron, 2003, 59, 8359.
51. K. Yagi and M. Irie, Chem. Lett., 2003, 848.
52. K. Higashiguchi, K. Matsuda and M. Irie, Angew. Chem. Int. Edn., 2003, 42, 3537.
53. M. Saito, Y. Yokoyama and Y. Yokoyama, Chem. Lett., 2003, 806.
54. K. Morimitsu, S. Kobatake, S. Nakamura and M. Irie, Chem. Lett., 2003, 858.
55. (a) Y. Asano, A. Murakami, T. Kobayashi, S. Kobatake, M. Irie, S. Yabushita and
S. Nakamura, J. Mol. Struct. (Theochem.), 2003, 625, 227; (b) Y. Asano,
A. Murakami, T. Kobayashi, S. Kobatake, M. Irie, S. Yabushita and S. Nakamura,
Chem. Abstr., 2003, 139, 92613.
56. Y. Yokoyama, H. Shiraishi, Y. Tani, Y. Yokoyama and Y. Yamaguchi, J. Am.
Chem. Soc., 2003, 125, 7194.
57. M. Saito, K. Musha, T. Ikejima, S. Ozawa, Y. Yokoyama and Y. Yokoyama,
Kobunshi Ronbunshu, 2003, 60, 581.
58. K. Yagi and M. Irie, Bull. Chem. Soc. Jpn., 2003, 76, 1625.
59. S. Takami, S. Kobatake, T. Kawai and M. Irie, Chem. Lett., 2003, 892.
60. J.J.D. de Jong, L.N. Lucas, R. Hania, A. Pugzlys, R.M. Kellogg, B.L. Feringa,
K. Duppen and J.H. van Esch, Eur. J. Org. Chem., 2003, 1887.
61. A. Peters, C. Vitols, R. McDonald and N.R. Branda, Org. Lett., 2003, 5, 1183.
62. B. Qin, R. Yao, X. Zhao and H. Tian, Org. Biomol. Chem., 2003, 1, 2187.
63. A. Mulder, A. Jukovic, F.W.B. van Leeuwen, H. Kooijman, A.L. Spek, J. Huskens
and D.N. Reinhoudt, Chem.-Eur. J., 2004, 10, 1114.
64. Y. Chen, D.X. Zeng and M.G. Fan, Org. Lett., 2003, 5, 1435.
65. T. Kawai, T. Iseda and M. Irie, J. Chem. Soc., Chem. Commun., 2004, 72.
66. Q.F. Luo, X.C. Li, S.P. Jing, W.H. Zhu and H. Tian, Chem. Lett., 2003, 1116.
67. E.A. Leo, J. Delgado, L.R. Domingo, A. Espinos, M.A. Miranda and R. Tormos,
J. Org. Chem., 2003, 68, 9643.
68. M. Yasuda, R. Kojima, H. Tsutsui, D. Utsunomiya, K. Ishii, K. Jinnouchi,
T. Shiragami and T. Yamashita, J. Org. Chem., 2003, 68, 7618.
69. D.W. Brousmiche, M.S. Xu, M. Lukeman and P. Wan, J. Am. Chem. Soc., 2003,
125, 12961.
70. N.P. Schepp and Y. Rodriguez-Evora, Can. J. Chem., 2003, 81, 799.
71. J. O’Reilly, S. Douin, S. Boye, N. Shafizadeh and D. Gauyacq, J. Chem. Phys.,
2003, 119, 820.
72. S.-H. Lee, Y.-Y. Lee, Y.T. Lee and X. Yang, J. Chem. Phys., 2003, 119, 827.
73. E.M. Nunez, A. Fernandez-Ramos, S.A. Vazquez, F.J. Aoiz and L. Banares,
J. Phys. Chem. A., 2003, 107, 7611.
74. K. Tanaka, M. Toshimitsu, K. Harada and T. Tanaka, J. Chem. Phys., 2004
120, 3604.
75. R. Gronheid, H. Zuilhof, M.G. Hellings, J. Cornelisse and G. Lodder, J. Org.
Chem., 2003, 68, 3205.
76. F.D. Lewis and X.B. Zuo, J. Am. Chem. Soc., 2003, 125, 8806.
77. K. McMahon and P.J. Wagner, Can. J. Chem., 2003, 81, 669.
78. N. Zhang and B. Zhou, CN 1379088, 13th November 2002.
79. R.M. Borg, D. Fanke and A. Vella, Can. J. Chem., 2003, 81, 723.
80. S. Asaoka, T. Wada and Y. Inoue, J. Am. Chem. Soc., 2003, 125, 3008.
81. (a) T. Murohoshi, K. Kaneda, M. Ikegami and T. Arai, Photochem. Photobiol.
Sci., 2003, 2, 1247; (b) T. Murohoshi, K. Kaneda, M. Ikegami and T. Arai, Chem.
Abstr., 2004, 140, 217177.
82. J.A. Pincock, Can. J. Chem., 2003, 81, 413.
83. R.S. Grainger and A. Patel, J. Chem. Soc., Chem. Commun., 2003, 1072.
84. (a) Z. Guennoun, I. Couturier-Tamburelli, N. Pietri and J.P. Aycard, Chem. Phys.
Lett., 2003, 368, 574; (b) Z. Guennoun, I. Couturier-Tamburelli, N. Pietri and
J.P. Aycard, Chem. Abstr., 2003, 138, 337585.
85. M.J. Krisch, J. Miller, L.J. Butler, H. Su, R. Bersohn and J. Shu, J. Chem. Phys.,
2003, 119, 176.
86. P.T. Howe and A. Fahr, J. Phys. Chem. A., 2003, 107, 9603.
87. J.D. De Sain and C.A. Taatjes, J. Phys. Chem. A., 2003, 107, 4843.
88. R.H. Qadiri, E.J. Feltham, N.H. Nahler, R.P. Garcia and M.N.R. Ashfold,
J. Chem. Phys., 2003, 119, 12842.
89. M. Kotani, S. Kobayashi, M. Mishima and Y. Hori, Chem. Lett., 2003, 294.
90. F. Wang and D.C. Neckers, J. Organomet. Chem., 2003, 665, 1.
91. S.K. Park and D.J. Baek, J. Photochem. Photobiol. A: Chem., 2003, 157, 15.
92. S.K. Park and D.J. Baek, J. Photochem. Photobiol. A: Chem., 2004, 163, 87.
93. P.J. Benites, R.C. Holmberg, D.S. Rawat, B.J. Kraft, L.J. Klein, D.G. Peters,
H.H. Thorp and J.M. Zaleski, J. Am. Chem. Soc., 2003, 125, 6434.
94. K.D. Lewis, D.L. Wenzler and A.J. Matzger, Org. Lett., 2003, 5, 2195.
95. Y. Tobe, R. Umeda, N. Iwasa and M. Sonoda, Chem.-Eur. J., 2003, 9, 5549.
96. O.S. Pyun, W.J. Yang, M.Y. Jeong, S.H. Lee, K.M. Kang, S.J. Jeon and B.R. Cho,
97. D. Armesto, M.J. Ortiz and A.R. Agarrabeitia, Mol. Supramol. Photochem.,
2003, 9, 1.
98. J.R. Scheffer and K. Vishnumurthy, Can. J. Chem., 2003, 81, 705.
99. C.M.P. Cecchi, R.M. de Barros, I.J.N. Lopes and F.Da S. Silva, Revista Universi-
dad Rural, Ser. Ciencias Exatas e da Terra, 2002, 21, 59.
100. K. Pitchumani, M. Warrier, L.S. Kaanumallee and V. Ramamurthy, Tetrahedron,
2003, 59, 5763.
101. S.Y. Lin, H.P. Hsieh, R.K. Peddinti and C.C. Liao, Tetrahedron Lett., 2003, 44, 8761.
102. Y.-S. Chen, Y. Song and X.-M. Yang, Gaodeng Xuexiao Huaxue Xuebao, 2002
23, 243.
103. L.M. Frutos, U. Sancho and O. Castano, Org. Lett., 2004, 6, 1229.
104. H.E. Zimmerman and T. Novak, J. Org. Chem., 2003, 68, 5056.
105. D. Armesto, O. Caballero, M.J. Ortiz, A.R. Agarrabeitia, M. Martin-Fontecha
and M.R. Torres, J. Org. Chem., 2003, 68, 6661.
106. (a) S. Koodanjeri, J. Sivaguru, A. Pradhan and V. Ramamurthy, Proc. Ind. Nat.
Sci. Acad., Pt A: Phys. Sci., 2002, 68, 453; (b) S. Koodanjeri, J. Sivaguru,
A. Pradhan and V. Ramamurthy, Chem. Abstr., 2003, 139, 149833.
107. (a) J. Sivaguru, S. Jockusch, N.J. Turro and V. Ramamurthy, Photochem. Photobiol.
Sci., 2003, 2, 1101; (b) J. Sivaguru, S. Jockusch, N.J. Turro and V. Ramamurthy,
Chem. Abstr., 2004, 140, 243427.
108. (a) Y. Wang, D.K. Luttrull, J.P. Dinnocenzo, J.L. Goodman, S. Farid and
I.R. Gould, Photochem. Photobiol. Sci., 2003, 2, 1169; (b) Y. Wang, D.K. Luttrull,
J.P. Dinnocenzo, J.L. Goodman, S. Farid and I.R. Gould, Chem. Abstr., 2004, 140,
303197.
109. M.A. O’Neill and F.L. Cozens, Can. J. Chem., 2003, 81, 647.
110. H. Ikeda, K. Akiyama, Y. Takahashi, T. Nakamura, S. Ishizaki, Y. Shiratori,
H. Ohaku, J.L. Goodman, A. Houman, D.D.M. Wayner, S. Tero-Kubota and
T. Miyashi, J. Am. Chem. Soc., 2003, 125, 9147.
111. H. Ikeda, Y. Hoshi, Y. Kikuchi, F. Tanaka and T. Miyashi, Org. Lett., 2004
6, 1029.
112. M. Newcomb and N. Miranda, J. Am. Chem. Soc., 2003, 125, 4080.
113. Y.-S. Chen, S. Ye and X.-M. Yang, Gaodeng Xuexiao Huaxue Xuebao, 2002, 23, 291.
114. (a) H. Maeda, Z. Li, T. Hirai and K. Mizuno, ITE Lett Batteries, New Tech. Med.,
2002, 3, 485; (b) H. Maeda, Z. Li, T. Hirai and K. Mizuno, Chem. Abstr., 2003,
139, 92609.
115. B.H.O. Cook and W.J. Leigh, Can. J. Chem., 2003, 81, 680.
116. (a) R.S.H. Liu, Huaxue, 2002, 60, 637; (b) R.S.H. Liu, Chem. Abstr., 2003, 139,
100674.
117. R.S.H. Liu and G.S. Hammond, Photochem. Photobiol. Sci., 2003, 2, 835.
118. (a) M. Garavelli, F. Ruggeri, F. Ogliaro, M.J. Bearpark, F. Bernardi, M. Olivucci
and M.A. Robb, J. Computational Chem., 2003, 24, 1357; (b) M. Garavelli,
F. Ruggeri, F. Ogliaro, M.J. Bearpark, F. Bernardi, M. Olivucci and M.A. Robb,
Chem. Abstr., 2003, 139, 179619.
119. C. Nonnenberg, S. Grimm and I. Frank, J. Chem. Phys., 2003, 119, 11585.
120. Y.S. Dou, B.R. Torralva and R.E. Allen, J. Phys. Chem. A., 2003, 107, 8817.
121. M. Squillacote, J.S. Wang and J.W. Chen, J. Am. Chem. Soc., 2004, 126, 1940.
122. J. Liu, E.L. Suits and K.J. Boarman, Tetrahedron Lett., 2003, 44, 8103.
123. H. Maeda, S. Nishioka and K. Mizuno, Tetrahedron Lett., 2003, 44, 6601.
124. J. Miyazaki and Y. Yamada, J. Mol. Structure, 2004, 692, 145.
125. A. Garcia-Granados, P.E. Lopez, E. Melguizo, A. Parra and Y. Simeo, Tetrahedron,
2004, 60, 1491.
126. K.C. Nicolaou, D.L.F. Gray and J.S. Tae, J. Am. Chem. Soc., 2004, 126, 613.
127. I. Skoric, A. Hutinec, Z. Marinic and M. Sindler-Kulyk, ARKIVOC, 200314), 87.
128. J. Saltiel, G. Krishnamoorthy, Z.N. Huang, D.H. Ko and S.J. Wang, Can. J. Chem.,
2003, 81, 673.
129. V.A. Kharlanov, W. Abraham and U. Pischel, J. Photochem. Photobiol. A: Chem.,
2004, 162, 213.
130. (a) Y.-Y. Gao, C.-J. You, J.-P. Chen and L. Yi, Ganguang Kexue Yu Guang
Huaxue, 2003, 21, 20; (b) Y.-Y. Gao, C.-J. You, J.-P. Chen and L. Yi, Chem.
Abstr., 2003, 139, 7060.
131. J.-y. Miao, L. Deng and T.-w. Tan, Beijing Huagong Daxue Xuebao, Ziran
Kexueban, 2003, 30, 39.
132. J. Saltiel, L. Cires and A.M. Turek, J. Am. Chem. Soc., 2003, 125, 2866.
133. S. Banerjee and S. Ghosh, J. Org. Chem., 2003, 68, 3981.
134. A. Elangovan, C.J. Wang and T.I. Ho, Chem. Lett., 2003, 1180.
135. L.-P. Zhang, B. Chen, L.-Z. Wu, C.-H. Tung, H. Cao and Y. Tanimoto, J. Phys.
Chem. A., 2003, 107, 3483.
136. L.-P. Zhang, B. Chen, L.-Z. Wu, C.-H. Tung, H. Cao and Y. Tanimoto, Chem.-Eur.
J., 2003, 9, 2763.
137. S. Inokuma, T. Sakaizawa, T. Funaki, T. Yonekura, H. Satoh, S. Kondo,
Y. Nakamura and J. Nishimura, Tetrahedron, 2003, 59, 8183.
138. (a) S. Inokuma, T. Funaki, D. Hara and J. Nishimura, Heterocycles, 2004, 63, 333;
(b) S. Inokuma, T. Funaki, D. Hara and J. Nishimura, Chem. Abstr., 2004, 140,
303653.
139. T. Funaki, S. Inokuma, H. Ide, T. Yonekura, Y. Nakamura and J. Nishimura,
140. S. Inokuma, T. Funaki and J. Nishimura, in: Cyclophane Chemistry for the 21st
Century, ed. H. Takemura, 2002, 149.
141. D. Aktah, D. Passerone and M. Parrinello, J. Phys. Chem. A., 2004, 108, 848.
142. X. Lu, J. Am. Chem. Soc., 2003, 125, 6384.
143. S. Inokuma, T. Funaki, S. Kondo and J. Nishimura, Tetrahedron, 2004, 60, 2043.
144. G.S. Papaefstathiou, T. Friscic and L.R. MacGillivray, J. Supramol. Chem., 2003,
2, 227.
145. X. Gao, T. Friscic and L.R. MacGillivray, Angew. Chem. Int. Ed., 2004, 43, 232.
146. N. Shan and W. Jones, Tetrahedron Lett., 2003, 44, 3687.
147. S. Nakatsuji, Y. Ogawa, H. Akutsu and J.I. Yamada, Bull. Chem. Soc. Jpn., 2003,
76, 1245.
148. S.P. Gromov, E.N. Ushakov, O.A. Fedorova, I.I. Baskin, A.V. Buevich,
E.N. Andryukhina, M.V. Alfimov, D. Johnels, U.G. Edlund, J.K. Whitesell and
M.A. Fox, J. Org. Chem., 2003, 68, 6115.
149. (a) J.-P. Zhuang and W.-Q. Zhang, Jiegou Huaxue, 2003, 22, 65; (b) J.-P. Zhuang
and W.-Q. Zhang, Chem. Abstr., 2003, 139, 21943.
150. J.-P. Zhuang and W.-Q. Zhang, Gaodeng Xuexiao Huaxue Xuebao, 2004, 25, 659.
151. (a) Y. Okada, M. Yoshida and J. Nishimura, Synlett., 2003, 1, 199; (b) Y. Okada,
M. Yoshida and J. Nishimura, Chem. Abstr., 2003, 139, 52998.
152. (a) D. Madhavan and K. Pitchumani, Photochem. Photobiol. Sci., 2003, 2, 95;
(b) D. Madhavan and K. Pitchumani, Chem. Abstr., 2003, 139, 133329.
153. M. Hara, S. Tojo and T. Majima, J. Phys. Chem. A., 2003, 107, 4778.
154. (a) S.-G. Lee and Y.-T. Park, Bull. Korean Chem. Soc., 2003, 24, 1241; (b) S.-G. Lee
and Y.-T. Park, Chem. Abstr., 2004, 140, 253283.
155. F. Ito and T. Nakanaga, J. Chem. Phys., 2003, 119, 5527.
156. (a) H. Nagai, H. Ohmura, F. Ito and T. Nakanaga, Chem. Phys. Lett., 2004, 383,
240; (b) H. Nagai, H. Ohmura, F. Ito and T. Nakanaga, Chem. Abstr., 2004, 140,
225624.
157. A.V. Komissarov and M.C. Heaven, J. Phys. Chem. A., 2003, 107, 10527.
158. D.E. Szpunar, Y. Liu, M.J. McCullagh, L.J. Butler and J. Shu, J. Chem. Phys.,
2003, 119, 5078.
159. T.Y. Kang, S.K. Shin and H.L. Kim, J. Phys. Chem. A., 2003, 107, 10888.
160. R. Marom, A. Golan, S. Rosenwaks and I. Bar, Chem. Phys. Lett., 2003, 378, 305.
161. P. Sharma, R.K. Vatsa, D.K. Maity and S.K. Kulshreshtha, Chem. Phys. Lett.,
2003, 382, 637.
162. Y.-R. Lee, C.-C. Chen and S.-M. Lin, J. Chem. Phys., 2003, 118, 10494.
163. S.-Y. Chiang, Y.-S. Fang, K. Sankaran and Y.-P. Lee, J. Chem. Phys., 2004, 120,
3270.
164. Y.-L. Li, C. Zhao, W.M. Kwok, X. Guan, P. Zuo and D.L. Phillips, J. Chem.
Phys., 2003, 119, 4671.
165. A.N. Tarnovsky, V. Sundstrom, E. Akesson and T. Pascher, J. Phys. Chem. A.,
2004, 108, 237.
166. B.J. Petro, E.D. Tweeten and R.W. Quandt, J. Phys. Chem. A., 2004, 108, 384.
167. Y. Tang, L. Jei, B.-F. Tang, R.-S. Zhu, S. Zhang and B. Zhang, Wuli Huaxue
Xuebao, 2004, 20, 344.
168. R.-S. Zhu, B.-F. Tang, L. Jei, Y. Tang, S. Zhang and B. Zhang, Optics Commun.,
2004, 235, 325.
169. P. Zou, J.N. Shu, T.J. Sears, G.E. Hall and S.W. North, J. Phys. Chem. A., 2004,
108, 1482.
170. W.M. Kwok, C.Y. Zhao, Y.L. Li, X.G. Guan, D.G. Wang and D.L. Phillips, J. Am.
Chem. Soc., 2004, 126, 3119.
171. J. Huang, D. Xu, J.S. Francisco and W.M. Jackson, J. Chem. Phys., 2003, 119,
3661.
172. X. Wang, Z. Tian, T. Shi, X. Shi, D. Yang and Q. Zhu, Chem. Phys. Lett., 2003,
380, 600.
173. M.Y. Chen, L.N. Paktar, M.D. Jan, A.S.Y. Lee and C.C. Lin, Tetrahedron Lett.,
2004, 45, 635.
174. Y.-R. Lee, C.-C. Chen and S.-M. Lin, J. Chem. Phys., 2004, 120, 1223.
175. N.K. Nair, M. van der Puy, D. Nalewajek, T.R. Demmin, A.J. Poss, D.E. Bradley,
I.R. Shankland and M.E. Cheney, U.S. US 6,551,469; Chem. Abstr., 2003, 138,
320904.
176. F. Gao, R.N. Compton and R.M. Pagni, J. Chem. Soc., Chem. Commun., 2003, 1584.
177. (a) Y. Sun, J.M. Yin, D.B. Gao, G.Y. Zhou and Y.P. Jia, Chin. Chem. Lett., 2003,
14, 575; (b) Y. Sun, J.M. Yin, D.B. Gao, G.Y. Zhou and Y.P. Jia, Chem. Abstr.,
2003, 139, 381169.
178. (a) N. Harato, Y. Tomisaka and A. Ogawa, Kidorui, 2003, 42, 68; (b) N. Harato,
Y. Tomisaka and A. Ogawa, Chem. Abstr., 2004, 140, 181138.
179. (a) J. Yin, D. Gao, J. Hu, G. Zhou, Y. Jia and X. Wang, Chinese Sci. Bull., 2003,
48, 2180; (b) J. Yin, D. Gao, J. Hu, G. Zhou, Y. Jia and X. Wang, Chem. Abs,
2004, 140, 163351.
180. C.Y. Oh, S.K. Shim, H.L. Kim and C.R. Park, J. Phys. Chem. A., 2003, 107, 4333.
181. (a) A.N. Santiago, C.A. Toledo and R.A. Rossi, J. Phys. Org. Chem., 2003, 16, 413;
(b) A.N. Santiago, C.A. Toledo and R.A. Rossi, Chem. Abstr., 2003, 139, 323181.
182. W. Zhou, Y. Yuan and J. Zhang, J. Chem. Phys., 2003, 119, 7179.
183. D. Dondi, M. Fagnoni, A. Molinari, A. Maldotti and A. Albini, Chem.-Eur. J.,
2004, 10, 142.
184. G. Mladenova, G. Singh, A. Acton, L. Chen, O. Rinco, L.J. Johnston and
E. Lee-Ruff, J. Org. Chem., 2004, 69, 2017.
Photochemistry of Aromatic Compounds
BY ANDREW GILBERT
University of Reading, Reading, UK
1 Introduction
Several reviews have been published within the year which are of general
relevance to the photoreactions of aromatic compounds. The subjects of these
reviews include photochemistry in ionic liquids1,2 and in isotropic and aniso-
tropic media,3 organic synthesis utilizing photoinduced electron-transfer reac-
tions,4 heteroatom-directed photoarylation processes,5 photochromism,6 and
photochemical molecular devices.7 Reviews more directly pertinent to the
sections in the present chapter include those of the photoisomerization of five-
membered heteroaromatic azoles,8 the photocycloaddition of benzene deriva-
tives to alkenes,9 Diels-Alder additions of anthracenes,10 advances in the syn-
thesis of polycyclic aromatic compounds,11 diarylethene-based photochromic
switches,12 the photo-Fries rearrangement,13 and the application of Diels-Alder
trapping of photogenerated o-xylenols to the synthesis of novel compounds.14 A
number of chapters in the two recently published handbooks of photochemistry
and photobiology15,16 and in the revised edition of the text on photochromism17
are also pertinent to the current subject matter.
2 Isomerization Reactions
The photoinduced cis-trans interconversions of 1,2-diarylethenes are reviewed

in Chapter 3 of this Volume. It is, however, pertinent to note here the study into
the geometric isomerization of cis 2,3-diphenylcyclopropane-1-carboxylic acid
derivatives.18 Such compounds, contrary to what is known about 1,2-di-
phenylcyclopropanes, are now reported to have triplet energies of approxi-
mately 311 kJ mol1, to undergo the less common adiabatic isomerization
to the trans isomers, to display emission from the electronically excited
1,3-diradical intermediates, and not to undergo intersystem crossing on direct
excitation.
A new mechanism involving Dewar benzene intermediates has been shown to
operate in the photoinduced electron-transfer promoted rearrangement of
2,2 0 ,3,3 0 -tetraphenylbicyclopropenyls (1).19 Thus irradiation (l 4 410 nm) of
91
(1) and 9,10-dicyanoanthracene (DCA) in degassed CH2Cl2 yields the two

Dewar isomers (2) and (3) and the arene (4) in time-dependent ratios, from
which it is deduced that, while (2) is stable under the reaction conditions, (3) is
the precursor of (4) following electron transfer to DCA. These results differ
from those reported earlier for such systems in acetonitrile solution.20
The vapour-phase photochemistry of 3,4,5-trideuteriopyridine is reported to

yield the positional isomers (5) and (6) by way of a route involving two
successive [1,3] sigmatropic shifts of nitrogen and an equilibrating mixture of
the azaprefulvenes (7) and (8), rather than by interconverting Dewar pyridine
intermediates, which would have lead to the (unobserved) 2,3,5-d3 pyridine.21
This work provides the first direct evidence that phototransposition of ring
atoms occurs in pyridine vapour. Earlier work on the photoisomerization of
1-methylpyrazoles indicated that the imidazole products arose from a compe-
tition between mechanisms involving N1–N2 bond cleavage (termed P4 pathway)
and electrocyclic ring closure to Dewar isomers (termed P6 and P7 pathways).
Further studies on these systems and monodeuterio derivatives have revealed
that the presence of a trifluoromethyl substituent promotes the P4 pathway,
resulting in, for example, the imidazoles (9) and (10) from (11) in a respective
ratio of 2:1 at 15% conversion.22 While both imidazoles are primary products,
(9) does undergo photoconversion to (10) via (12) under the reaction conditions.
Pyrazole photoisomerizations have also been the subject of an ab initio study,
from which it is concluded that the S1 state can yield the Dewar isomer and the
corresponding triplet state, which then forms the 1,2-diradical leading to
isomerization.23 While this behaviour is deduced for 1,5-dimethylpyrazole, the
T1 state of 1-methyl-5-phenylpyrazole cannot seemingly yield the corresponding
diradical, and isomerization occurs only from the Dewar isomer.
Both aniline and 4-methylpyridine are reported to undergo photorearrange-

ment on 193 nm irradiation, to give seven-membered ring isomers, which then
undergo internal H-atom migration and rearomatization prior to dissocia-
tion.24 Using similar experimental conditions, the same research group has also
shown that azulene isomerizes to naphthalene and eventually undergoes dis-
sociation by way of the H-atom elimination channel.25
Several previous reports have described various features of the reversible
photoisomerization of 1,8a-dihydroazulene dicarbonitriles to vinylheptafulvenes.
The first time-resolved investigation of this ring-opening reaction has now been
reported and, using sub-30 fs transient absorption spectroscopy, prominent
workers in this area have determined that the ring opening of (13) to (14)
occurs within 1.2 ps, which is followed by internal conversion of S1 (14) to S0
(14) in 13 ps.26
3 Addition Reactions
The intramolecular meta photocycloaddition of ethenes to the benzene ring has

proved to be a useful key step in the synthesis of a number of complex molecular
skeletons. It is well appreciated that the photoreactivity of these bichromophores
is maximized for non-conjugated systems, such as derivatives of 5-phenylpent-1-
ene, in which the two interacting moieties are separated by three molecular units
in the tether. The synthetic scope of the procedure would be significantly
improved if the reaction could be extended to efficient intramolecular cyclizat-
ions for bichromophores having longer tether units and to systems with chem-
ically reactive tethers for subsequent elaboration or removal. Both of these
aspects have been examined with the bichromophores (15), but, although
intramolecular meta photocycloaddition was observed for (15, X ¼ CH2 or
SiMe2), the chemical yields of the expected 1,6-bridged dihydrosemibullvalene
adducts (16) were low (7–19%).27 As the authors note, however, these reactions
with four units and removable tethers do have merit, as they provide an
approach to complex molecular systems not readily accessible by conventional
means. The molecular constraints to approach of the aryl and alkenyl chro-
mophores in the 2-alkenylnaphtha-4-chromanones (17) are severe, but, although
a complex mixtures does result on their irradiation (l 4 330 nm) in methanol
solution, the highly functionalized polycyclic compound (18) was isolated in
20% yield.28 Interestingly, as outlined in Scheme 1, the formation of (18) can be
envisaged by either 1,2- or 1,4- intramolecular cycloaddition to the naphthalene
moiety. The sole process from irradiation (l 4 330 nm) of cyclohexane solutions
of 1,3-dimethylthymine and naphthalene is reported to arise from 1,4-addition
giving (19), with high stereoselectivity, and in 72% yield at 46% consumption of
the pyrimidine.29 The same research group has also described the photoreaction
between 6-chloro-1,3-dimethyluracil and phenanthrenes or pyrene.30 Both (2p þ
2p) cycloaddition and substitution occur, giving from phenanthrene, for exam-
ple, the products (20) and (21), respectively, in ratios which are dependent on the
solvent. Thus, while there is no reaction in cyclohexane solution, the respective
yields of (20) and (21) in benzene are 10 and 30%, which change in the presence
of small amounts of trifluoroacetic acid to 55 and 5%. Similar addition at the
9,10-positions of methyl 9-phenanthrenecarboxylate has been observed for
cholesteryl cinnamate (22).31 The photoadduct (23) is isolated in 74% yield
(de 8%) along with 9% of the cis isomer. The photodimerization of cholesteryl
9-phenanthrenecarboxylate, giving solely the head-to-tail syn isomer (24) in 55%
yield (de 8%) is also described in this report. Highly regioselective (2pþ2p)
cycloaddition has been reported for 4-methyl-1,2,4-triazoline-3,5-dione at the
cis-1 [6,6] ethene bond of C60 and several fullerene derivatives from 420 nm
irradiation of solutions in tetrachloroethane.32
Scheme 1
The photochemical Diels-Alder reactions of anthracene with fumarodinitrile

and 1,4-benzoquinone have been studied in chloroform solution.33 Not sur-
prisingly, the addition occurs in competition with dimerization of the arene and
proceeds by way of electron transfer from anthracene to the dienophiles. The
radical ion pair has been detected by transient absorption spectroscopy, and the
resulting diradical precursor of adduct formation from the quinone was
observed by ESR at 77 K. 2,7-Dibromotropone is reported to undergo
(8pþ4p) photoaddition to 9,10-dicyanoanthracene in benzene–methanol
(9:1), giving (25) as the primary adduct which is then proposed to react with
methanol and water (solvent contaminant) to yield the final product (26).34 In
contrast, 2-bromotropone and the anthracene in CH2Cl2 solution afford the
substitution products (27) (62%) and (28) (25%).
Scheme 2
The photocycloaddition chemistry of pyridines substituted with electron-

donor and electron-acceptor groups at the 2- and 3- positions continues to be
exploited. The results of irradiation of such pyridines in the presence of
2-cyanofuran have now been described.35 The yields of the (4pþ4p) cycload-
ducts (29) and (30), the pyridine dimer (31) and the transposition isomer (32)
are dependent on the level of methyl substitution on the heteroarene and are
given in Scheme 2. Other photocycloadditions to heteroarenes reported within
the year include the reactions of benzodithiophene (33) with butadiyne deriv-
atives and dimethyl acetylene dicarboxylate, giving low yields of (34) and (35)
respectively, the latter from photorearrangement of the primary adduct (36).36
The (2pþ4p) photocycloaddition of indoles (37) to cyclohexa-1,3-dienes (38) is
sensitized by the aromatic ketones (39), and yields (14–46%) of the exo and
endo isomers of the adduct (40) in ratios which are dependent on the substitu-
ents on the addends.37
The radical addition cyclization which occurs on 350 nm irradiation of mixed

acetonitrile solutions of N,N-dimethylaniline and menthyloxyfuranone (41) is
reported to be diastereoselective and is initiated by photoinduced electron
transfer from the amine to the semiconductors TiO2, SnO2, ZnS or SiC.38 The
major and minor adducts are proposed to be formed by the route outlined in
Scheme 3 and are accompanied by products derived from the radical produced
on partial reduction of (41).
Irradiation of the enantiomorphous co-crystals obtained from mixed solu-
tions of 9-methylbenz[c]acridine and diphenylacetic acid is reported to yield the
photodecarboxylation-addition product (44) as essentially a racemic mixture,
along with diphenylmethane and 1,2-tetraphenylethane.39 The lack of selecti-
vity in the formation of (44) from the co-crystals is considered to arise from the
molecular arrangement of the reactants in the lattice, and the same products are
also formed from irradiation of the acridine and the acid in acetonitrile
solution.
4 Substitution Reactions
The effects of variation of pH, nucleophile concentration and light intensity on

the photoinduced substitution of m-nitroaniline by nitrite ion have been
reported, and a tentative mechanism has been proposed for the process.40
Good yields (39–93%) of 2,4,6-tribromoanilines can seemingly be obtained by
irradiation (l 4 340 nm) of nitrobenzene and some derivatives in concentrated
hydrobromic acid.41 The quantum yield for the reaction with nitrobenzene is
0.16, and this is little affected by a 3-carboxy group, but the presence of a 3- or
4-hydroxy substituent has a detrimental effect on the reaction, which leads the
authors to suggest that electron transfer to the nitroarene np* triplet from the
bromide ion, is the primary process. Photonucleophilic substitution reactions
of nitroanisoles continue to attract interest, and the research group that earlier
Scheme 3
described the exclusive formation of methoxyphenols from irradiation of 2- and

4-nitroanisoles in the presence of cyclodextrins,42 now report that, using the
same experimental conditions, photoamination of 1,2-dimethoxy-4-nitroben-
zene by ammonia, methylamine or hexylamine leads to regioselective displace-
ment of the methoxy group which is para to the NO2 substituent, in contrast to
the solution reaction which predominantly yields the 3-amino-nitro com-
pound.43 The authors interpret this change in regioselectivity in terms of a
mechanistic shift from a SN2Ar* process in the latter case, in which the nitro
group is meta-directing, to a route involving electron transfer from the amino
nucleophile to the excited state nitroanisole [SN(ET)Ar*] in the presence of the
cyclodextrins. The size of the H-D isotope effect observed in the 1,4-dicyano-
naphthalene photosensitized cyanation of biphenyls (see Scheme 4) is reported
to be dependent on the concentrations of both the substrate and the cyanide ion
as well as the ionic strength of the medium.44 These experimental observations
are considered to originate from intermolecular electron exchange between the
biphenyl and its radical cation, in competition with attack of the cyanide ion.
From an investigation of the photoreactions of 4-chlorophenol and 4-chlo-
roanisole in a variety of solvents, it has been shown that reductive dehalogen-
ation is the principal process, which proceeds by a homolytic pathway in
cyclohexane and a heterolytic route in methanol or trifluoroethanol.45 The
100 Photochemistry, 36, 2007, 91–132
Scheme 4
latter path has been exploited as a convenient route to triplet 4-hydroxy- and 4-
methoxyphenyl cations, which in the presence of p-nucleophiles (e.g. 2,3-
dimethylbut-2-ene or benzene) can provide a medium-to-good yield access to
arylated compounds: these reactions are summarized in Scheme 5. The forma-
tion of products such as (45) from irradiation of cyanobenzenes and 2,3-
dimethylbut-2-ene in methanol solution is a commonly observed process
(photo-NOCAS), but as noted this year this reaction can be suppressed by
acrylonitrile, and then (46) predominates.46 The irradiation of 1-bromonaph-
thalene and sodium sulfide in DMSO solution followed by quenching with
methyl iodide is reported to yield 1-methylthionaphthalene (16%), bis (1-
naphthyl) sulfide (17.5%) and naphthalene (42%) by a radical chain mecha-
nism.47 A similar reaction is also observed with the thiourea anion, and this
gives the 1-methylthionaphthalene in a 50% yield after quenching. Many
accounts have described the attack of photochemically generated radicals on
aromatic compounds, but the recent report of generating such species with
electron withdrawing groups by Se–CF2 bond cleavage in (47) and their
subsequent reaction with arenes and heteroarenes to give, for example (48) in
reasonable yield, is worthy of note in this section.48
Photochemistry, 36, 2007, 91–132 101
Scheme 5
5 Cyclization Reactions
Photoinduced 6p-electrocyclization occurs for a wide variety of aromatic systems

and attracts considerable research activity, which, over the years, has resulted in
a number of commercial applications particularly in the areas of photochromism
and molecular switches. Investigations into stilbene derivatives have a long
history in this area. trans 3,3 0 ,5,5 0 -Tetramethoxystilbene yields the cis isomer on
irradiation, which then undergoes photocyclization and oxidation to 2,4,5,7-
tetramethoxyphenanthrene (49), and no reversal of the geometric isomerization
is observed.49 Similarly, irradiation of (50) obtained by Hofmann degradation of
1,2,3,4-tetrahydro-2,2-dimethylisoquinolinium iodides (51) with methanolic
KOH, affords (52),50 and 6p-photoelectrocyclization of (53) gives good yields
102 Photochemistry, 36, 2007, 91–132
of (54), which provides access to the 2-azachrysene (55) in three further steps.51
This type of process with the dihydroisoquinolin-1(2H)-one derivative (56) is a
key step in the first total synthesis of the tetrasubstituted 1,2,3,4-tetra-
hydronaphtho[2,1-f]isoquinoline (57).52 The photoconversion of cyclohexane
or acetonitrile solutions of trans (58) directly into 1-hydroxychrysene in good
yields (one-photon absorption) has provided evidence for the involvement of an
adiabatic trans* to cis* isomerization,53 but in aqueous solvents (MeCN:H2O,
1:1) trans 3-hydroxystilbene affords solely the hydration products (59) and (60),
in marked contrast to the 2- and 4-hydroxystilbenes, which undergo trans-cis
photoisomerization.54 Further examples of the use of photocyclizations of
mono- and distyryl substituted polynuclear arenes in the synthesis of helicenes
have been published.55 In these examples, irradiation of toluene solutions of (61)
and (62) with iodine in the presence of propylene oxide as an HI scavenger, gives
62–96% and 70–90% of the [5]- and [7]carbohelicenes (63) and (64), respectively,
depending on the substituents. Mechanistic studies into the photochromism of
arene [e]-annelated dimethyldihydropyrenes (65) have been described, and ap-
preciably larger quantum yields for the ring opening reaction than for simpler
dihydropyrenes have been observed, which, the authors suggest, makes such
compounds as (65) more useful as photoswitchable units.56 Stilbenes with
functionality on the ethene moiety are not commonly used in this 6p-photo-
electrocyclization process. It is, however, now reported that irradiation of 1,
2-diaryl-1-tosylethenes (66) in the presence of base gives the corresponding
phenanthrenes and heterocyclic analogues in yields which vary with the base
employed (DBU, Et3N, or CaCO3) and the solvent (THF, benzene, CH2Cl2, or
methanol).57 For example, 3,6-dimethylphenanthrene is formed in 95% yield
from irradiation of (67) in THF in the presence of five equivalents of DBU; the
mechanism is considered to involve base-induced elimination of p-toluenesulfinic
acid from the intermediate 9-tosyl-4a,4b-dihydrophenanthrene.
Photochemistry, 36, 2007, 91–132 103
104 Photochemistry, 36, 2007, 91–132
Photochemistry, 36, 2007, 91–132 105
Again this year considerable activity has been focused on the photochromic
properties of 1,2-diheteroarylethenes, and two groups have reported the results
of theoretical studies on these systems. The role of conical intersections in these
processes58 and whether the photochromism can be explained by the reaction
path alone59 have both received attention. At present, the heteroarylethenes
favoured for application in molecular devices would seem to be those based on
1,2-bis(methylthienyl) and 1,2-bis(methylbenzothienyl)perfluorocyclopentenes,
and much effort has been devoted to assessing the influence of structural
modification and physical state on their photochromic properties and charac-
teristics. For example, the asymmetric compounds (68) and (69), having different
sites of attachment to the two heteroarenes, have been investigated and found to
be sensitive to wavelengths in the 400–500 nm region and to have good fatigue
resistance,60 and for (70) the change of the commonly-used methyl substituents at
the 2- and 2 0 -positions by isopropyl groups reduces the efficiency of the cyclizat-
ion and requires higher temperatures for the thermal reversal.61 The introduction
of cyano groups in place of the 2,2 0 -methyl substituents in (71), however,
increases the quantum yield of cycloreversion by approximately 30-fold.62
Russian workers have developed methods to introduce functional groups
(e.g. halogen, –CHO, –CO2H) at the 4- and 4 0 -positions of the thienyl moieties
with the purpose of producing photochromic condensation polymers,63 and a
further report into the exceptionally high thermal stability of the cyclized isomer
(72) of (73) also notes that the efficiency of the photochemical cycloreversion is
comparable to that of the corresponding dithienyl compound.64 The influence of
linking photochromic dithienylperfluorocyclopentenes has been investigated with
such diverse systems as (74), (75), (76) and (77). Multicolour photochromism has
106 Photochemistry, 36, 2007, 91–132
been is observed in (74) using 313, 365 and 436 nm irradiation, and by varying
the exposure time colour changes in solution through yellow, green and blue have
been accomplished, although only one of the two units is cyclized at any one
time.65 Again for (75) only one of the open forms cyclizes, and this results in a
change from colourless to dark blue,66 and (76) is reported to exhibit reversible
photochromism both in solution and in the bulk amorphous phase.67 In contrast
to most other systems, the blue colouration induced on 313 nm irradiation of
hexane solutions of (77) arises from the presence of both the mono- and
dicyclized isomers, and furthermore (77) also exhibits photochromism as a single
crystal.68 Interestingly, these dithienyl chromophores are aligned almost perpen-
dicular to each other in the crystal and, using linearly polarized light, one of the
photoactive units in (77) can be selectively ring closed. Indeed, a number of
reports have been published in the year outlining the photochemistry of di-
thienylperfluorocyclopentenes in the bulk amorphous phase, crystals, co-crystals,
nanoparticles and films. For example, irradiation (334 nm) of (78) in the bulk
amorphous phase produced a new absorption band at 600 nm and analysis
showed that the closed isomer was formed with a diastereoisomeric excess of
25%.69 The optically active photochromic dithienylethene (79) forms two crys-
talline phases (a- and b-) both of which undergo 6p-photoelectrocyclization, and,
while the a-phase showed no diastereoselectivity in the closure, only the (S,R,R)
diastereomer (80) was formed on irradiation of the b-phase.70 The achiral
compound (81) is reported to undergo absolute asymmetric photocyclization
in chiral crystals, and the two enantiomers of both the open and the closed forms
are observed not to be interconverted.71 The three different types of di-
thienylethenes (82), (83) and (84) form novel two- and three-component multi-
colour photochromic crystals and in the latter, by using radiation of appropriate
wavelengths, the crystals are turned yellow, orange, red, purple, blue, green or
black.72 The authors note that such multicoloured photochromic crystals may
have application in full-colour displays and other optoelectronic devices. Other
workers have also investigated the potential of three-component systems as
multi-wavelength photochromic storage devices.73 The derivative (85) having
two pentafluorophenyl groups is reported to afford stoichiometric 2:1 and 1:1
co-crystals with benzene and naphthalene, respectively, by using intermolecular
non-covalent sandwich aryl-perfluoroaryl interactions.74 Both these species dis-
play the photochromism of the dithienylethene unit, but the absorptions of the
photoisomers in the co-crystals differ and depend on the conformations of the
photoactive molecules. Nevertheless, although the dithienyl ethene pair (85) and
(86) also has the possibility of aryl-perfluoroaryl interactions and do form
alternate nanolayers of molecular sheets in the 1:1 stoichiometric co-crystal,
there is no evidence for the p–p stacking of the molecules.75 Both (85) and (86)
undergo photochromism in one-component crystals but in the co-crystals only
(86) photoreacts and then only to a conversion of 20%, indicating energy transfer
from (85) to (86) in the crystal. Nanoparticles of the dithienylethene (87) are
formed by a reprecipitation method, but the aggregation resulted in a decrease in
the efficiency of the cyclization process and in a blue shift in the absorption of the
closed isomer.76 A self-assembled monolayer technique has been used to prepare
Photochemistry, 36, 2007, 91–132 107
gold nanoparticles capped with the photochrome (88), which is reported to

undergo the expected photochromic activity regardless of the environment.77
Incorporation of dithienylperfluorocyclopentenes in DNA-quarternary ammo-
nium complex transparent self-standing films does, however, have varying effects
on the photocyclization process and although derivatives without hydroxy
groups behave similarly to their reactions in solution, the presence of such
functionality as in (89) markedly slows the reaction in the film.78 Further reports
have appeared on the electrochemical ring closure and ring opening reactions of
photochromic bis(terthiophene)perfluorocyclopentene,79 and other workers have
shown that (90) also undergoes cyclization when its excited state is accessed by
electron-carrier injection.80
108 Photochemistry, 36, 2007, 91–132
Photochemistry, 36, 2007, 91–132 109
The influence on the photochromism in dithienylethene systems of replacing

the favoured perfluorocylopentene moiety by other cyclic ethene units has
attracted the attention of a number of research groups. Dutch workers have
shown that the use of the perhydrocyclopentene unit as in (91) has little effect on
the photochromic behaviour of (92) but note that in situations where fatigue
resistance and thermal stability are critical, the fluorinated moiety would be
preferable.81 The cyclization quantum yield of (93) is reported to increase in the
presence of metal ions,82 and more detailed accounts have been published of the
interesting application of the dithienylcyclopentene-tethered b-cyclodextrins (94)
as photoswitchable hosts for meso tetrakis(4-sulfonatophenyl)porphyrin.83,84
110 Photochemistry, 36, 2007, 91–132
Several groups have described the photochromic activities of

diheteroarylmaleimides. Of the dithienyl compounds (95), that with R1 ¼ CN
and R2 ¼ NO2 displayed photochromism even in polar solvents (MeCN,
EtOH), but the derivatives with R1 ¼ Ph or OMe and R2 ¼ H were inactive,85
whereas the dithieno[3,2-b]pyrroles (96) with an N-substituted imide moiety are
reported to undergo cyclization in acetonitrile solution.86 Interest in the closure
reaction of the bis indolylmaleimides (97) arises from the need to access
biologically active, naturally occurring indolocarbazole alkaloids such as re-
beccamycin (98).87 Indeed, irradiation of (97) in the presence of iodine gave the
required indolo[2,3-a]pyrrolo[3,4-c]carbazoles (99) in yields of 84–90%. By
using a related photocyclization, French workers have successfully synthesized
a new family of isogranulatimide analogues in which the 7-azaindole moiety
replaces the indole unit.88 Thus irradiation of (100) in acetonitrile solution
affords the cyclized products (101) and (102) in respective yields of 21 and 19%,
with a further 24% of (101), without the BOC protection. Oxidation and
deprotection of the isolated products gave the two isomeric analogues of
isogranulatimides A (103) and B (104). The novel dithienylethene (105) has
been shown to act both as a photochromic and as an acidichromic yellow dye,
as outlined in Scheme 6,89 and the diheteroaryl derivatives (106), having a 2,
5-dihydrothiophene bridge, have been synthesized although as yet there is no
account of their photochemical properties.90 In contrast to other dithienyl
ethenes, the dithienyl[1,3]dithiol-2-ones (107) and (108) undergo photo-
decarbonylation rather than photocyclization and this leads to the 1,4-dithine
(109) from the former isomer, while (108) produces the thieno[3,4-c]dithiine
(110) in 76% yield by way of a unique ring cleavage.91 The photochemical
reactivity of the two dithienylethene systems (111) and (112), having fixed
conformations but varying molecular rigidity, has been examined in acetonitrile
solution, and although (111) undergoes reversible photochromism the more
constrained compound (112) is reported to be unreactive.92 Excellent fatigue
resistance in repeat cycle photochromism and high thermal stability of the
coloured isomer are reported for the novel 1-(isopropylidene)-2-(thien-3-yl)
perfluorocyclopentene (113), which has a quantum yield of cyclization to (114)
with 313 nm radiation of 0.43 and of cycloreversion with 405 nm radiation of
Photochemistry, 36, 2007, 91–132 111
0.16.93 Such 6p-electrophotocyclization is commonly observed for a variety of

1-arylbuta-1,3-dienes and is also the basic process for the photochromism of
fulgides and fulgimides. The mechanism of these reactions has been subjected
to a theoretical investigation using PM3 semiempirical quantum chemistry and
MECI CI methods, and the results are reported to support the mechanism
112 Photochemistry, 36, 2007, 91–132
Scheme 6
evolved from experimental observations.94 The molecular conformational

changes in relation to the crystal structure of the photochromic system based
on the 3-furylfulgide (115) have been studied.95 Single crystals of (115) turn
from yellow to red on irradiation, but during the cyclization process giving
(116) the crystallinity is lost. In addition, x-ray diffraction analysis of crys-
tallized (116) has been carried out and is reported to provide the first
determination of the molecular conformation and crystal structure of such
cyclized compounds. Fulgides of type (117) in PMMA matrices exhibit
photochromism which is reported to display no fatigue in over 450 writing-
erasing cycles and hence is suggested to have the characteristics required for
halographic applications.96 A novel class of photochromic (Z)-4-ox-
azolylfulgimides (118) has been synthesized and, not surprisingly, the absorp-
tion characteristics of the ring opened and ring closed isomers are found to be
dependent on the nature of the aryl substituent.97 6p-Photocyclization of the
1-arylbuta-1,3-diene moiety in curcumin (119) in non-degassed solution
produces 2 0 -hydroxy-5 0 ,6 0 -benzochalcone (120) along with the secondary
photoisomer (121) as well as the degradation products benzaldehyde and
cinnamaldehyde.98 The authors note that the cyclization of (120) to give (121)
is the unique example of the photoconversion of a diarylheptanoid iso-
merizing to a flavanoid. Interestingly, non-conjugated phenylpolyalkenes of
appropriate structure as in (122), for example, undergo intramolecular
photocyclization in aqueous acetonitrile and in the presence of an elec-
tronacceptor couple such as 1,4-dicyanotetramethylbenzene and biphenyl,
to give the polycyclic compound (123) in 22–25% yield.99 This procedure has
the virtue of providing a convenient pathway to polycyclic compounds in a
single operation.
Photochemistry, 36, 2007, 91–132 113
114 Photochemistry, 36, 2007, 91–132
Photochemistry, 36, 2007, 91–132 115
Further details have been published concerning the efficient photocyclization

of the syn rotomer of 2-vinylbiphenyls to give 8a,9-dihydrophenanthrene inter-
mediates (124), which undergo a rapid sigmatropic shift to yield the 9,10-
dihydrophenanthrenes (125).100 The photochemistry of stilbenylpyrroles (126)
in benzene or acetonitrile solution is reported to give a new approach to indole
(127) and isoindole (128) derivatives (respective yields 33 and 5%), and, as the
authors note, the reaction provides the first example of intramolecular addition
of a pyrrole molecule to the ethene moiety of a stilbene.101 The treatment of bis
indole and the keto lactam (129) with BF3 Et2O affords a 57% yield of (130),
which undergoes efficient 6p-photocyclization and thereby gives a simple direct
access to the indolo[2,3-a]carbazole alkaloid staurosporinone (131).102 The
indolinylphenylethenes (132) undergo electrocyclization of the 1-aza-1,3,5-hexa-
triene moiety, giving (133), which give good yields of (134) following
oxidation.103 Both 2-vinylstyryl-furans (135) and pyrroles (136) undergo photo-
induced cyclization processes. The intermediate (137) from (135) with R2 ¼ H
has been previously trapped with oxygen to give the hydroperoxide (138),104 but
the derivatives with R ¼ Me, Br, or –CH ¼ CH2 are now reported to give both
exo and endo isomers of the benzobicyclo[2.1.1]hexenes (139) and the phenan-
threnes (140).105 The former arise by (2pþ2p) photocycloaddition while the
latter are explained by a mechanism involving a (4þ2) process followed by
dehydration, as outlined in Scheme 7. The photobehaviour of (136), not
surprisingly, basically follows that described104 for (135; R2 ¼ H) and gives
the tetrahydromethanobenzo[4,5]cyclohepta[1,2-b]pyrroles (141), albeit in low
yields.106
116 Photochemistry, 36, 2007, 91–132
The photocyclizations of 1-allyloxy- and 1-allylamino-2-halogenoarenes giving

dihydrofurans and indoles respectively has been observed to be remarkably
enhanced by the presence of enolate ions as an entrainment reagent.107 For
example, (142) is obtained in 55% yield from irradiation of 1-allyloxy-2-chloro-
benzene but this is increased to 91% when the CH3COCH2 ion is present, and
similarly under the latter conditions the yield of (143) from (144) is greater than
96%. Three reports have appeared within the year describing various features of
the photocyclization reactions of aryl-substituted N-acyl-a-dehydroalanine deriv-
atives (145), which yield both isoquinolines (146) and 1-azetines (147). The
influence of meta substituents on the process has been reported, and while both
the 6- and 8-substituted isomers of (146) are formed for R ¼ Me, Cl and CF3, the
preference for the former is explained in terms of steric effects, whereas a meta
methoxy group exerts both steric and electronic influences, giving 6-substituted-
2-quinolinone and isoquinolinone derivatives.108 This reaction has been extended
to other substituted derivatives of (145), and the mechanism for formation of (146)
and (147) has been outlined and is depicted in Scheme 8.109 Both processes occur
with 1-naphthyl analogues of (145), and for the conversion of (148), having a chiral
auxiliary, into the 3,4-dihydrobenzo[f]quinolinones isomers in the presence of a
Photochemistry, 36, 2007, 91–132 117
Scheme 7
tertiary amine, the magnitude of the diastereomeric excess for (S,S)-(149) varied
from 0 to 55% dependent on the characteristics of the amine and the solvent.110
118 Photochemistry, 36, 2007, 91–132
Scheme 8
The antimicrobial additive Triclosan (150) is commonly detected in surface

waters and worryingly has now been shown to undergo a process of dehydro-
halogenation-cyclization to yield 2,8-dichlorodibenzo-p-dioxin (151) in both
buffered and natural water.111 The photocyclization of phenyl-1,4-benzoqui-
none giving 2-hydroxybenzofuran has been subjected to time-resolved photo-
acoustic calorimetric and flash photolytic investigations, and a long-lived
intermediate, suggested to be a diradical, has been confirmed.112 The well-
known photoconversion of diphenylamine derivatives into carbazoles has been
studied theoretically for Ph2NCH3nPhn (n ¼ 0–3) using semiempirical PM3
Photochemistry, 36, 2007, 91–132 119
methods, and while the cyclization is predicted for Ph2NMe, N–C bond
cleavage is considered to be favoured for Ph2NCPh3, which is in agreement
with experimental findings.113 The photocyclization of N-methylated enamin-
ones (152) has been investigated as a key step in a synthetic approach to
analogues of indoloquinoline and pyridocarbazole alkaloids.114 The formation
of (153) by this route allowed the preparation in three further steps of the
pyridopyrroloquinolines (154) for in vitro testing.114
6 Dimerization Processes
The (4pþ4p) photodimerization reactions of anthracene and its derivatives

continue to attract research interest for a variety of reasons. The process with
9-methyl- and 9-chloroanthracenes has been used to monitor structural trans-
formations in crystals. In the former derivative, the cell volume increases at the
start of the dimerization process and decreases subsequently, and the product
molecules are not fixed during the reaction but are reported to move smoothly in
a manner that includes a rotational component.115 It is noted for 9-chloro-
anthracene that the symmetry of the dimer is defined by the orientation of the
monomer, but that the molecules of the monomer in the crystal pack differently
from those in the recrystallized dimer.116 Anthracenes 2,6-disubstituted with
decyloxy or (Z)-dec-4-enyloxy chains are liquid crystal materials exhibiting
smectic A or C phases, in which the photodimerization yield is low compared to
the solution phase reaction, mainly as a result of the instability of the dimer
at the high temperatures of the mesophases.117 The photodimerization of
1-(anthracen-9-ylmethyl)-3-ethylimidazolium iodide (155), giving the head-
to-tail dimer (156), has been the subject of two reports within the year,118,119
and the process with 2-anthracenecarboxylate in an aqueous buffer (pH 7) has
been shown to be subject to enantiodifferentiation using bovine serum albu-
min.120 In this case, the regioselectivity in the formation of the four (4pþ4p)
dimers (157)–(160) is changed from head-to-tail to head-to-head by adding the
120 Photochemistry, 36, 2007, 91–132
albumin, and this also yields the achiral dimers (158) and (159) with enantio-
meric excesses of 29 and 41%, respectively, at 5% conversion. The hydrogen-
bonded molecular assembly (161) has been generated by using the head-to-tail
photodimerization of the 9-substituted anthracene (162),121 while intramolecu-
lar dimerization of the two anthracene moieties in the resorcin[4]arenes (163)
with 350 nm radiation can yield thermally stable (4pþ4p) adducts, and thereby
produce a system with potential as a photoswitch.122 Irradiation of an argon-
degassed cyclohexane solution of the soluble tetracene (164) is reported to give
the head-to-tail and head-to-head dimers (165) and (166), respectively, each in
yields of 20%.123 Differentiation between the structures of the two dimer
isomers is achieved by the excimer fluorescence from (166) and the naphthalene
monomer fluorescence from (165), and the authors note that this is the first
account of photodimerization for substituted tetracenes. Not surprisingly, irra-
diation of 9-(phenyloxymethyl)anthracene does not yield an intramolecular
cycloaddition product, and instead bond cleavage occurs.124
Photochemistry, 36, 2007, 91–132 121
7 Lateral Nuclear Shifts
The photo-Fries reaction of 2-benzoyl-4-benzoyloxyphenol (167) affords 2,

3- and 2,5-dibenzoyl-1,4-dihydroxybenzenes (168) and (169) in respective
yields of 48 and 19% on 254 nm irradiation,125 and similarly both 2- and
122 Photochemistry, 36, 2007, 91–132
4-rearrangement products are formed from the 5,8-dihydro-1-naphthyl esters

(170) in relative and absolute yields which are very dependent on the nature of
the R group.126 Two examples have been reported within the year which well
illustrate the potential for encapsulation mediation of the photo-Fries rear-
rangement. Thus, while irradiation of 1-naphthyl phenyl acetates (171) in
hexane solution gives eight products from this b-cleavage process, excitation
of the solid inclusion complex of (171) in g-cyclodextrin yields essentially only
the 2-substituted naphthols (172), which is attributed to the cyclodextrin cavity
inducing conformational and translational restrictions on both the naphthyl
ester and the reaction intermediates.127 The same research group has reported
similar effects by mediating the photoreactions of the same esters in the zeolite
NaY.128 In this case, the high selectivity in product formation is considered to
arise from the alkali metal ions in the zeolite restricting the mobility of the
primary radical pair. Furthermore, these workers also report that the dibenzyl
ketones (173), which yield solely decarbonylation products in solution, also
afford the rearrangement isomers (174) on irradiation in heavy atom (Cs, Tl)
exchanged zeolites. The 313 nm irradiation at 401C of substituent blocked
naphthyl esters has allowed Japanese workers to isolate, for the first time, labile
cyclohexadienones which are the type of intermediates postulated in the photo
Fries rearrangement.129 Thus the 4-substituted rearrangement product (175)
was obtained in 22% yield from (176), and, although the 2-isomer (177) was not
isolated, it was detected by HPLC at low reactant conversion. Irradiation of
(178) under similar conditions, however, did induce rearrangement to give (179)
with the acyl group at the 2-position. The two isomeric acylcyclohexadienones
have been shown to have quite different photochemical reactivities and, while
(175) gives both the starting ester (176) and the 2-rearranged product (177) as
well as the naphthol on 313 nm irradiation, (179) under the same experimental
conditions proved to be photostable.130 The photo-Fries rearrangement of
dibenzofuran-2-yl ethanoate (180) has been investigated under both Lewis acid
catalysis and on irradiation.131 Formation of the rearrangement products (181)
and (182) is reported to be more efficient under the latter conditions and with
CH2Cl2 as the solvent. Similarly, both the 1-acyl- and 3-acyl-2-hydroxy-
carbazoles (183) and (184), respectively, are formed on either 254 or 313 nm
irradiation of the 2-acyloxycarbazoles (185) in various solvents, and the
authors suggest this photo Fries rearrangement as a convenient step in the
synthesis of carbazole alkaloids.132 Phenylurea herbicides in aqueous solution
are reported to display photochemical behaviour which is markedly dependent
on the nature and position of substituents on the arene, and, although
photosolvolysis dominates for halogenated derivatives, the photo-Fries reac-
tion is observed in other cases.133 Such rearrangement of the p-toluenesulfon-
anilides (186), giving the 2- and 4-amino-substituted diaryl sulfones (187) and
(188), respectively, appears to be a general process, the yields of which
(38–72%) are increased by N-alkylation of the sulfonanilides but are not
drastically reduced by electron withdrawing substituents on the N-phenyl
ring.134 Since 2- and 4-aminoaryl sulfones are not easily accessible, this route
would seem to have synthetic merit.
Photochemistry, 36, 2007, 91–132 123
124 Photochemistry, 36, 2007, 91–132
The photochemistry of diphenylether in methanol solution has been reported

to be affected by ultrasound and, while the rate of rearrangement to 2-
hydroxybiphenyl remains unchanged by sonication, that of the 4-hydroxy
isomer is decreased and phenol production is increased.135
8 Miscellaneous Photochemistry of Aromatic Systems
The photochemistry of many aromatic compounds which have a methyl or

substituted methyl group in a 2-position to a carbonyl or nitro functionality
(H-abstraction) or a hydroxyl group (formal loss of water) is frequently dom-
inated by the formation of quinone methides as reaction intermediates. Many
examples of trapping these structural moieties by Diels-Alder reactions have
been used in synthetic pathways. The reaction of such intermediates from
substituted benzaldehydes with some 17 dienophiles illustrates the considerable
potential of the process, added to which, yields of the adducts are generally
good.136 For example, trapping the hydroxy-o-quinodimethane species (189)
from the aldehyde (190) with methyl methacrylate in toluene solution gives an
81% yield of a 2:1 mixture of diastereoisomers (191).137 The formation of the
adduct (192) by irradiation of the tetrahydro-2-oxoquinoline-5-aldehyde (193)
with acrylonitrile illustrates the molecular complexity that can readily be
achieved from this photoenolization and, furthermore, irradiation of these
particular systems at 601C in the presence of the chiral complexing agent
(194) produced adducts with excellent enantioselectivity (91–94% ee).138 The
photoactive [4-(11-mercaptoundecyl)-phenyl](2-methylphenyl)methanone (195)
has been co-adsorbed with other thiols to the surface of monolayer-protected
Photochemistry, 36, 2007, 91–132 125
clusters.139 The dienol moieties from (195) are reported to be formed efficiently
on irradiation and readily trapped with dimethyl acetylene dicarboxylate. The
photoremoval of the 1-[2-(2-hydroxyalkyl)phenyl]ethanone protecting group for
carboxylic acids is considered to arise by intramolecular hydrogen abstraction in
(196) to form the quinone methide (197),140 and a similar photodeprotection
mechanism has also been reported for irradiation of 2,5-dimethylphenacyl esters
(198).141 Evidence has been presented that the mechanism of the photorelease of
methanol from 2-nitrobenzyl methyl ether arises by initial formation of the
quinone methide analogue (199) in a pathway outlined in Scheme 9.142 The
quinone methide (200) is proposed to be involved in the selective phototrans-
formation of hydroxy-substituted aromatic nitrones (201) into N,N-diaryform-
amide derivatives (202), but in this case the intermediate is formed by ring
opening of the primary photoproduct, the oxaziridine (203), as shown in Scheme
10.143 Chromene photochromism is known to proceed by formation of quinone
methides, and an interesting example of the process described this year is that
observed for the novel materials (204) bearing a monoazacrown ether moiety,
which allows interaction with metal ions.144
Scheme 9
126 Photochemistry, 36, 2007, 91–132
Scheme 10
Photochemistry, 36, 2007, 91–132 127
Irradiation of hydroxybiphenyl alkenes and alcohols is reported to yield novel

biphenyl quinone methides such as (205) from (206), and in aqueous acetonitrile
solution it is these intermediates that undergo attack by water to yield the
observed photohydration products.145 Similar photoinduced proton taut-
omerization in 2-hydroxyphenazine (207) yields (208), which is the origin of
the observed photochromism at 77 K in this and related systems.146 Irradiation
of 1,4,4,4-tetraphenylbut-2-en-1-one (209) in benzene or acetonitrile solution
leads to rearrangement and the formation of trans 1-benzoyl-2,2,3-tri-
phenylcyclopropane (210).147 This reaction is a new example of the concerted
mechanism in which an aryl group migrates synchronously with formation of a
cyclopropane ring, as much earlier described by Zimmermann and Hancock.148
Dibenzobarrelenes are known to undergo photorearrangement to dibenzocyclo-
octadienes, and such a reaction of (211) in THF solution to give a 95% yield of
(212) has been used in a synthetic route to a tetraphenylene derivative.149 The
photoelimination of indan from (213) has provided access to the highly strained
dibenzotetrakisdehydro[12]annulene (214), which was trapped by its Diels Alder
adduct with furan.150
128 Photochemistry, 36, 2007, 91–132
References
1. C.M. Gordon, Nato Sci. Ser., II Math. Phys. Chem., 2003, 92, 365.
2. R.M. Pagni, ACS Symp. Ser., 2003, 856, 344.
3. V. Ramamurthy and K.S. Schanze, Mol. Supramol. Photochem., 2003, 9, 408.
4. R.G. Harvey, Curr. Org. Chem., 2004, 8, 303.
5. J.P. Dittami, J. Photosci., 2003, 10, 21.
6. S. Kobatake and M. Irie, Ann. Rep. Prog. Chem., Section C: Phys. Chem., 2003, 99,
277.
7. V. Balzani, Photochem. Photobiol. Sci., 2003, 2, 459.
8. J.W. Pavlik, Progr. Heterocycl. Chem., 2003, 15, 37.
9. N. Hoffmann, Synthesis, 2004, 481.
10. J.C.C. Atherton and S. Jones, Tetrahedron, 2003, 59, 9039.
11. R.G. Harvey, Curr. Org. Chem., 2004, 8, 303.
12. H. Tian and S. Yang, Chem. Soc. Rev., 2004, 33, 85.
13. M.A. Miranda and F. Galindo, Mol. Supramol. Photochem., 2003, 9, 43.
14. M.A. Meada, Spectrum, 2003, 16, 22.
15. W.M. Horspool and F. Lenci (ed.), CRC Handbook of Organic Photochemistry and
Photobiology, 2nd edn., CRC Press, Boca Raton, Florida, 2004.
16. H.S. Nalwa (ed.), Handbook of Photochemistry and Photobiology, American
Scientific Publishers, Stevenson Ranch, California, 2003.
17. H. Dürr and H. Bouas-Laurent (ed.), Photochromism: Molecules and Systems
Revised Edition, Elsevier Science, Amsterdam, 2003.
Photochemistry, 36, 2007, 91–132 129
18. J. Sivaguru, S. Jockusch and N.J. Turro, Photochem. Photobiol. Sci., 2003, 2,
1101.
19. H. Ikeda, Y. Hoshi, Y. Kikuchi, F. Tanaka and T. Miyashi, Org. Lett., 2004, 6,
1029.
20. A. Padwa, S.I. Goldstein and R.J. Rosenthal, J. Org. Chem., 1987, 52, 3278.
21. J.W. Pavlik and S. Laohhasurayotin, Tetrahedron Lett., 2003, 44, 8109.
22. J.W. Pavlik, T.I.N. Ayudhaya, C.R. Pandit and S. Tantayanon, J. Heterocycl.
Chem., 2004, 41, 61.
23. M. D’Auria and R. Racioppi, Lett. Org. Chem., 2004, 1, 12.
24. C.-M. Tseng, Y.A. Dyakov, C.-L. Huang, A.M. Mebel, S.H. Lin, Y.T. Lee and
C.-K. Ni, J. Am. Chem. Soc., 2004, 126, 8760.
25. M.-F. Lin, C.-L. Huang, Y.T. Lee and C.-K. Ni, J. Chem. Phys., 2003, 119, 2032.
26. V. de Waele, M. Beutter, U. Schmidhammer, E. Riedle and J. Daub, Chem. Phys.
Lett., 2004, 390, 328.
27. C.S. Penkett, P.W. Byrne, B.J. Teobald, B. Rola, A. Ozanne and P.B. Hitchcock,
Tetrahedron, 2004, 60, 2771.
28. G.P. Kalena, P. Pradhan, V.S. Puranik and A. Banerji, Tetrahedron Lett., 2003, 44,
2011.
29. K. Ohkura, T. Ishihara, Y. Nakata and K. Seki, Heterocycles, 2004, 62, 213.
30. K. Ohkura, S. Uchiyama, M. Sato, J.M. Diakur and K. Seki, Heterocycles, 2003,
59, 459.
31. H. Maeda, A. Horiuchi, N. Koshio and K. Mizuno, Chem. Lett., 2004, 33, 966.
32. L. Ulmer, C. Siedschlag and J. Mattay, Eur. J. Org. Chem., 2003, 3811.
33. S. Fukuzumi, T. Okamoto and K. Ohkubo, J. Phys. Chem. A, 2003, 107, 5412.
34. A. Mori, H. Kawakami, N. Kato, S.-P. Wu and H. Takeshita, Org. Biomol. Chem.,
2003, 1, 1730.
35. M. Sakamoto, T. Yagi, S. Kobaru, T. Mino and T. Fujita, Tetrahedron Lett., 2004,
45, 4437.
36. B. Wex, B.R. Kaafarani, A.G. Oliver, J.A.K. Bauer and D.C. Neckers, J. Org.
Chem., 2003, 68, 8258.
37. J. Perez-Prieto, S.-E. Stiriba, M. Gonzales-Bejar, L.R. Domingo and M.A. Miranda,
Org. Lett., 2004, 6, 3905.
38. S. Marinkovic and N. Hoffmann, Eur. J. Org. Chem., 2004, 3102.
39. H. Koshima, A. Nakata, M. Nagano and H. Yu, Heterocycles, 2003, 60, 2251.
40. S. Bahedia, R. Ameta, M. Jain and S.C. Ameta, Int. J. Chem. Sci., 2003, 1, 203.
41. B.P. McIntyre, B.D. Coleman and G.G. Wubbels, Tetrahedron Lett., 2004, 45,
7709.
42. M.C.D. Manickam, K. Pitchumani and C. Srinivasan, J. Photochem. Photobiol. A:
Chem., 2002, 149, 131.
43. M.C.D. Manickam, K. Pitchumani and C. Srinivasan, Proc. Indian Acad. Sci.,
Chem. Sci., 2003, 115, 273.
44. R. Gronheid, J. Baggerman and G. Lodder, J. Phys. Chem. A, 2003, 107, 7675.
45. S. Protti, M. Fagnoni, M. Mella and A. Albini, J. Org. Chem., 2004, 69, 3465.
46. R.M. Borg, D. Franke and A. Vella, Can. J. Chem., 2003, 81, 723.
47. J.E. Argueello, L.C. Schmidt and A.B. Penenory, ARKIVOC, 2003, (10), 411.
48. S. Murakami, S. Kim, H. Ishii and T. Fuchigami, Synlett., 2004, 815.
49. A. Momotake, M. Uda and T. Arai, J. Photochem. Photobiol., A, 2003, 158, 7.
50. S.V. Kini and M.M.V. Ramana, Tetrahedron Lett., 2004, 45, 4171.
51. M.C. Pampin, J.C. Estevez, R.J. Estevez, M. Maestro and L. Castedo, Tetrahedron,
2003, 59, 7231.
130 Photochemistry, 36, 2007, 91–132
52. M.C. Pampin, J.C. Estevez, R.J. Estevez and L. Castedo, ARKIVOC, 2003, (15),
29.
53. P. Bortolus, G. Galiazzo, G. Gennari, I. Manet and G. Marconi, Photochem.
Photobiol. Sci., 2004, 3, 689.
54. T. Murohoshi, K. Kaneda, M. Ikegami and T. Arai, Photochem. Photobiol. Sci.,
2003, 2, 1247.
55. R. El Abed, B. Ben Hassine, J.-P. Genet, M. Gorsane and A. Marinetti, Eur. J.
Org. Chem., 2004, 1517.
56. M.A. Sheepwash, T.R. Ward, Y. Wang, S. Bandyopadhyay, R.H. Mitchell and C.
Bohne, Photochem. Photobiol. Sci., 2003, 2, 104.
57. J.F. Almeida, L. Castedo, D. Fernandez, A.G. Neo, V. Romero and G. Tojo, Org.
Lett., 2003, 5, 4939.
58. Y. Asano, A. Murakami, T. Kobayashi, A. Goldberg, D. Guillaumont, S. Yabushita,
M. Irie and S. Nakamura, J. Am. Chem. Soc., 2004, 126, 12112.
59. M. Boggio-Pasqua, M. Ravaglia, M.J. Bearpark, M. Garavelli and M.A. Robb,
J. Phys. Chem. A, 2003, 107, 11139.
60. F. Sun, F. Zhang, H. Guo, X. Zhou and F. Zhao, Tetrahedron, 2003, 59, 7615.
61. S. Kobatake and M. Irie, Chem. Lett., 2003, 32, 1078.
62. K. Morimitsu, S. Kobatake, S. Nakamura and M. Irie, Chem. Lett., 2003, 32, 858.
63. M.M. Krayushkin and A. L. Rusanov, Polymer Preprints, 2003, 44, 367.
64. S. Takami, S. Kobatake, T. Kawai and M. Irie, Chem. Lett., 2003, 32, 892.
65. K. Higashiguchi, K. Matsuda and M. Irie, Angew. Chem., Int. Ed., 2003, 42, 3537.
66. K. Yagi and M. Irie, Chem. Lett., 2003, 32, 848.
67. A. Tomari, T. Yamaguchi, N. Sakamoto, Y. Fujita and M. Irie, Chem. Lett., 2004,
33, 1380.
68. S. Kobatake, S. Kuma and M. Irie, Bull. Chem. Soc. Jpn., 2004, 77, 945.
69. T. Yamaguchi, K. Nomiyama, M. Isayama and M. Irie, Adv. Mater., 2004, 16, 643.
70. S. Yamamoto, K. Matsuda and M. Irie, Org. Lett., 2003, 5, 1769.
71. S. Yamamoto, K. Matsuda and M. Irie, Angew. Chem., Int. Ed., 2003, 42, 1636.
72. M. Morimoto, S. Kobatake and M. Irie, J. Am. Chem. Soc., 2003, 125, 11080.
73. G.-S. Qi, J.-X. Xiao, R. Liu, P.-J. Jiang, P. She and D.-Y. Xu, Wuli Xuebao, 2004,
53, 1076.
74. M. Morimoto, S. Kobatake and M. Irie, Cryst. Growth Design, 2003, 3, 847.
75. M. Morimoto, S. Kobatake and M. Irie, Photochem. Photobiol. Sci., 2003, 2, 1088.
76. F. Sun, F. Zhang, F. Zhao, X. Zhou and S. Pu, Chem. Phys. Lett., 2003, 380, 206.
77. K. Matsuda, M. Ikeda and M. Irie, Chem. Lett., 2004, 33, 456.
78. M. Saito, K. Musha, T. Ikejima, S. Ozawa, Y. Yokoyama and Y. Yokoyama,
79. A. Peters and N.I. Branda, Proc. Electrochem. Soc., 2003, 12, 85.
80. T. Tsujioka and H. Kondo, Appl. Phys. Lett., 2003, 83, 937.
81. J.J.D. de Jong, L.N. Lucas, R. Hania, A. Pugzlys, R.M. Kellog, B.L. Feringa,
K. Duppen and J.H. van Esch, Eur. J. Org. Chem., 2003, 1887.
82. B. Qin, R. Yao, X. Zhao and H. Tian, Org. Biomol. Chem., 2003, 1, 2187.
83. A. Mulder, A. Jukovic, F.W.B. van Leeuwen, H. Kooijman, A.L. Spek, J. Huskens
and D.N. Reinhoudt, Chem. - Eur. J., 2004, 1114.
84. A. Mulder, A. Jukovic, J. Huskens and D.N. Reinhoudt, Org. Biomol. Chem.,
2004, 2, 1748.
85. T. Yamaguchi and M. Irie, Chem. Lett., 2004, 33, 1398.
86. M.M. Krayushkin, V.N. Yarovenko, S.L. Semenov, I.V. Zavarzin, A.Y. Martynkin
and B.M. Uzhinov, Russ. J. Org. Chem., 2003, 52, 1814.
Photochemistry, 36, 2007, 91–132 131
87. G.M. Reddy, S.-Y. Chen and B.-J. Uang, Synthesis, 2003, 497.
88. B. Hugon, B. Pfeiffer, P. Renard and M. Prudhomme, Tetrahedron Lett., 2003, 44,
4607.
89. Q. Luo, X. Li, S. Jing, W. Zhu and H. Tian, Chem. Lett., 2003, 32, 1116.
90. M.M. Krayushkin, V.N. Yarovenko, S.L. Semenov, I.V. Zavarzin, A.Y. Martynkin
and B.M. Uzhinov, Russ. J. Org. Chem., 2003, 39, 1656.
91. S.J. Roberts-Bleming, G.L. Davies, M. Kalaji, P.J. Murphy, A.M. Celli, D. Donati
and F. Ponticelli, J. Org. Chem., 2003, 68, 7115.
92. M.M. Krayushkin, S.N. Ivanov, B.V. Lichitskii, A.A. Dubinov, L.G. Vorontsova,
Z.A. Starikov and A.Y. Martynkin, Russ. J. Org. Chem., 2004, 40, 79.
93. S.M. Shrestha, H. Nagashima, Y. Yokoyama and Y. Yokoyama, Bull. Chem. Soc.
Jpn., 2003, 76, 363.
94. S.-L. Li, Z.-H. Li and W.-L. Feng, Beijing Huagong Daxue Xuebao, 2003, 30, 62.
95. L. Khedhiri, A. Corval, R. Casalegno and M. Rzaigui, J. Phys. Chem. A., 2004,
108, 7473.
96. Y. Chen, C. Wang, M. Fan, B. Yao and N. Menke, Opt. Mater., 2004, 26, 75.
97. J. Xiao, Y. Han, Y. Chen, W. Li and M.-G. Fan, Chinese J. Chem., 2004, 22, 100.
98. A. Sundaryono, A. Nourmamode, C. Gardrat, S. Grelier, G. Bravic, D. Chasseau
and A. Castellan, Photochem. Photobiol. Sci., 2003, 2, 914.
99. V. Rosales, J. Zambrano and M. Demuth, Eur. J. Org. Chem., 2004, 1798.
100. F.D. Lewis and X. Zuo, Photochem. Photobiol. Sci., 2003, 2, 1059.
101. N. Basaric, Z. Marinic and M. Sindler-Kulyk, Tetrahedron Lett., 2003, 44, 7337.
102. S.P. Gaudencio, M.M. M. Santos, A.M. Lobo and S. Prabhakar, Tetrahedron
Lett., 2003, 44, 2577.
103. O.A. Fedorova, Y.V. Fedorov, E.N. Andryukhina, S.P. Gromov, M.V. Alfimov
and R. Lapouyade, Org. Lett., 2003, 5, 4533.
104. I. Skoric, N. Basaric, Z. Marinic and M. Sindler-Kulyk, Heterocycles, 2001, 55,
1889.
105. I. Skoric, A. Hutinec, Z. Marinic and M. Sindler-Kulyk, ARKIVOC, 2003, (14), 87.
106. N. Basaric, Z. Marinic and M. Sindler-Kulyk, J. Org. Chem., 2003, 68, 7524.
107. S.E. Vaillard, A. Postigo and R.A. Rossi, J. Org. Chem., 2004, 69, 2037.
108. K. Maekawa, H. Kajiwara, Y. Iseya, T. Igarashi and T. Sakurai, Heterocycles,
2003, 60, 637.
109. H. Hoshina, K. Maekawa, K. Taie, T. Igarashi and T. Sakurai, Heterocycles, 2003,
60, 1779.
110. K. Maekawa, K. Kubo, T. Igarashi and T. Sakurai, Tetrahedron, 2004, 60, 1183.
111. D.E. Latch, J.L. Packer, W.A. Arnold and K. McNeil, J. Photochem. Photobiol.,
A., 2003, 158, 63.
112. N. Chattopadhyay, C. Serpa, L.G. Arnaut and S.J. Formosinho, Ind. J. Chem.
Section A: Inorg. Bio-inorg. Phys. Theo. Anal. Chem., 2003, 42A, 1827.
113. M.F. Budyka, THEOCHEM., 2003, 629, 127.
114. P.-J. Aragon, A.-D. Yapi, F. Pinguet, J.-M. Chezal, J.-C. Teulade, J.-P. Chapat
and Y. Blache, Chem. Pharm. Bull., 2004, 52, 659.
115. I. Turowska-Tyrk and E. Trzop, Acta Cryst., Section B: Structural Sci., 2003, 59, 779.
116. I. Turowska-Tyrk and K. Grzesniak, Acta Cryst., Section C: Cryst. Structure
Commun., 2004, 60, 146.
117. S. Mery, D. Haristoy, J.-F. Nicoud, D. Guillon, H. Monobe and Y. Shimizu,
J. Mater. Chem., 2003, 13, 1622.
118. Q.-X. Liu, H.-B. Song, F.-B. Xu, Q.-S. Li, X.-S. Zeng, X.-B. Leng and Z.Z. Zhang,
J. Chem. Res. S, 2003, 445.
132 Photochemistry, 36, 2007, 91–132
119. Q.X. Liu, H.B. Song, F.B. Xu, Q.S. Li and Z.Z. Zhang, Acta Cryst., Section E:
Structure Rep. Online, 2004, E60, 674.
120. T. Wada, M. Nishijima, T. Fujisawa, N. Sugahara, T. Mori, A. Nakamura and
Y. Inoue, J. Am. Chem. Soc., 2003, 125, 7492.
121. M. Ikegami, I. Ohshiro and T. Arai, J. Chem. Soc., Chem. Commun., 2003, 1566.
122. C. Schaefer and J. Mattay, Photochem. Photobiol. Sci., 2004, 3, 331.
123. J. Reichwagen, H. Hopf, A. Del Guerzo, J.-P. Desvergne and H. Bouas-Laurent,
Org. Lett., 2004, 6, 1899.
124. C.-M. Gao, D.-R. Cao and L. Zhu, Ganguang Kexue Yu Guang Huaxue, 2004, 22, 103.
125. K.K. Park, H.J. Lee, E.H. Kim and S.K. Kang, J. Photochem. Photobiol., A, 2003,
159, 17.
126. K. Sriraghavan and V.T. Ramakrishnan, Tetrahedron, 2003, 59, 1791.
127. S. Koodanjeri, A.R. Pradhan, L.S. Kaanumalle and V. Ramamurthy, Tetrahedron
Lett., 2003, 44, 3207.
128. M. Warrier, L.S. Kaanumalle and V. Ramamurthy, Can. J. Chem., 2003, 81, 620.
2004, 33, 254.
2004, 33, 256.
131. A.M.A.G. Oliveira, A.M.F. Oliveira-Campos, M.M.M. Raposo, J. Griffiths and
A.E.H. Machado, Tetrahedron, 2004, 60, 6145.
132. S.M. Bonesi, L.K. Crevatin and R. Erra-Balsells, Photochem. Photobiol. Sci., 2004,
3, 381.
133. A. Amine-Khodja, A. Boulkamh and P. Boule, Photochem. Photobiol. Sci., 2004, 3,
145.
134. K.K. Park, J.J. Lee and J. Ryu, Tetrahedron, 2003, 59, 7651.
135. A. Gaplovsky, J. Donovalova, S. Toma, B. Jakubikova and R. Mracnova, Chem.
Papers, 2003, 57, 250.
136. K.C. Nicolaou, D.L.F. Gray and J. Tae, J. Am. Chem. Soc., 2004, 126, 613.
137. K.C. Nicolaou and D.L.F. Gray, J. Am. Chem. Soc., 2004, 126, 607.
138. B. Grosch, C.N. Orlebar, E. Herdtweck, M. Kaneda, T. Wada, Y. Inoue and
T. Bach, Chem. – Eur. J., 2004, 2179.
139. A.J. Kell, C.C. Montcalm and M.S. Workentin, Can. J. Chem., 2003, 81, 484.
140. W.N. Atemnkeng, L.D. Louisiana, P.K. Yong, B. Vottero and A. Banerjee, Org.
Lett., 2003, 5, 4469.
141. J. Literik, S. Relich, P. Kulhanek and P. Klan, Mol. Diversity, 2003, 7, 265.
142. Y.V. Il’ichev, M.A. Schwoerer and J. Wirz, J. Am. Chem. Soc., 2004, 126, 4581.
143. H. Kondo, K. Tanaka, K. Kubo, T. Igarashi and T. Sakurai, Heterocycles, 2004,
63, 241.
144. S.A. Ahmed, M. Tanaka, H. Ando, H. Iwamoto and K. Kimura, Eur. J. Org.
Chem., 2003, 2437.
145. D.W. Brousmiche, M. Xu, M. Lukeman and P. Wan, J. Am. Chem. Soc., 2003,
125, 12961.
146. K. Ogawa, M. Miura, T. Nakayama and J. Harada, Chem. Lett., 2003, 32, 840.
147. J.R. Scheffer and K. Vishnumurthy, Can. J. Chem., 2003, 81, 705.
148. H.E. Zimmermann and K.G. Hancock, J. Am. Chem. Soc., 1968, 90, 3749.
149. C.W. Hui, T.C.W. Mak and H.N.C. Wong, Tetrahedron, 2004, 60, 3523.
150. Y. Tobe, I. Ohki, M. Sonoda, H. Niino, T. Sato and T. Wakabayashi, J. Am.
Chem. Soc., 2003, 125, 5614.
Photo-oxidation and Photo-reduction
BY NIALL W.A. GERAGHTY

Chemistry Department, National University of Ireland, Galway, Ireland
1 Introduction
Photo-oxidation and photo-reduction remain among the most active areas of

photochemical research, with interest in general centring on systems involving
photo-induced electron transfer (PET), heterogeneous photo-oxidation and
photooxygenation. The interest in PET results from the ongoing efforts
directed towards producing systems capable of artificial photosynthesis,
whereas that in heterogeneous oxidation systems, particularly TiO2, is occa-
sioned by their value in photodegrading potential pollutants. Although there
continues to be interest in photooxygenation as a clean or green oxidation
process, much of the work in this area remains linked to issues relating to
photodynamic therapy (PDT). A number of major new photochemistry books
have been published in the period covered by this review1,2 and a new edition of
an older work has also appeared.3 Although these books deal with a variety of
topics in photochemistry, photobiology and photophysics, many of their
chapters constitute useful and up-to-date reviews of areas relating to photo-
oxidation and photo-reduction. A number of these reviews, and of those
published elsewhere, are of general interest in the context of the sub-divisions
used in this review. Thus reviews dealing with PET reactions in organic
chemistry in general,4 with the control elements in PET reactions,5 and with
appropriate and readily accessible computational methods for such reactions,6
have been published. A discussion of synthetic organic chemistry in mesopo-
rous silicas,7 which deals with the photodecarboxylation of a-hydroxy car-
boxylic acids, the oxidation of arylmethyl halides and alcohols and the
oxidative cleavage of styrene, and a review which deals with the application
of PET reactions in heterocyclic chemistry,8 have also appeared. Reflecting the
continuing interest in using zeolites as a medium for photochemical reactions,
photo-oxidations,9,10 PET,11 and the potential for achieving selectivity, includ-
ing enantioselectivity, in this constrained environment12 have been reviewed. A
comparison of PET reactions of organic substances with oxygen in zeolite
nanocavities and in solution has been provided13 as has a review of some of the
most recent achievements in the field of photochemical molecular devices,
133
134 Photochemistry, 36, 2007, 133–204
including a discussion of those involving PET.14 Light-induced charge transfer

(CT) at phthalocyanine surfaces and its technological applications,15 and the
reactivities of various Ti-based photocatalysts in the context of a range of
different reactions have also been reviewed.16
2 Reduction of the Carbonyl Group
Many of the carbonyl group reductions reported involve PET from an amine.
Thus the mechanism of the photo-reduction of benzophenone by N,N-di-
methylaniline has been discussed with particular reference to experimental
results and theoretical models relating to the dynamics of proton transfer in the
radical ion pair formed by PET.17 The photo-reduction of o-benzoquinones,
such as (1), in the presence of p-bromo-N,N-dimethylaniline is reported18 to
give pyrocatechols and hydroxyphenyl ethers (Scheme 1), the former being
produced as a result of the disproportionation of two semi-quinone radicals.
The hydroxyphenylethers subsequently form pyrocatechols as a result of a
thermal decomposition. Quinones feature in a number of other recent papers
relating to the photo-reduction of the carbonyl group. The effect, for example,
of alcohols and amines on the intermediates involved in the photo-reduction of
p-benzoquinones has been studied.19 The reduction step leading to the forma-
tion of hydroquinones involves electron transfer (ET) in the presence of amines
and hydrogen transfer in the case of alcohols. Photo-reduction processes
involving 1,4-naphthoquinone in water have also been investigated using
nanosecond flash photolysis and product analysis (Scheme 2).20 A number of
transients were observed, to which structures (2) and (3) were assigned. An acid
catalysed hydrogen-atom migration subsequently gives 1,4,5- and 1,4,7-
trihydroxynaphthalene, which in turn form the observed products, 1,4-di-
hydroxynaphthalene and 5- and 7-hydroxy-1,4-naphthoquinone, following a
fast oxido-reduction with 1,4-naphthoquinone. PET between the S1 state of the
dihdroxyquinones (4) and (5) and a range of aromatic and aliphatic amines has
been studied.21 A significant difference was observed in the diffusion controlled
fluorescence-quenching constants obtained for the aromatic and the aliphatic
amines, the latter being about 46% lower. The results were rationalized on the
basis that there is an orientational restriction on the encounter complexes
involving the aliphatic amines, arising from the shape of their HOMOs. Finally,
photo-induced hydrogen abstraction by the carbonyl group of homoquinones
But
OH
But NMe2 But
O OH
λ > 500nm But O
+ +
C 6H 6
But O But OH N Br
Br Me
(1)
Scheme 1
Photochemistry, 36, 2007, 133–204 135
O OH O
O OH
+
HO H OH OH OH OH O
hv (2) H+ NQ
+
H 2O + O OH O
HO +
O HO HO OH
NQ H
OH OH O
(3)
Scheme 2
O OH O
O OH Me
Ph
Ph
Me
O OH O
O OH (5) (6)
(4)
Me
N X
O R3 (7) or (8) O HO
R4 hv, THF R3
N R1 R1 R4
O BDMAP
Me R 2 R2
(7) X = 2-OH
(8) X = 4-OH
Scheme 3
such as (6) and their participation in PET with amine and arene donors have
been reviewed.22
In relation to other carbonyl systems, it is reported that the amines 2-(2 0 -
hydroxyphenyl)-1,3-dimethylbenzimidazoline (7) and 2-(4 0 -hydroxyphenyl)-
1,3-dimethylbenzimidazoline (8) promote the PET reactions of a,b-epoxy
ketones forming b-hydroxy ketones (Scheme 3).23 The reaction involves an
initial single electron transfer (SET) to the carbonyl group, and overall the
amines act as the formal donors of two hydrogen atoms. The use of 1,6-
bis(dimethylamino)pyrene (BDMAP) as a sensitizer allows the reaction to be
extended to epoxy ketones that could not be sufficiently activated by direct
irradiation using pyrex filtered light. A consideration of the conversion of a,b-
epoxy ketones to b-hydroxy ketones forms part of a review which focuses on
the PET generation of ketyl radicals and their subsequent rearrangement.24 The
review also considers the PET reactions of a-bromomethyl ketones and
136 Photochemistry, 36, 2007, 133–204
O R1 R1
sunlight 2
R R2
1 2
R R 2-propanol HO OH
R1 = Ph, R2 = H
Yield (isolated) = 70-96% R1 = 4-ClC6H4, R2 = CH3
R1 = R2 = Ph
R1 = Ph, R2 = CH3
Scheme 4
4-tribromomethylcyclohexa-2,5-dienones. In general the photo-reduction of

ketones and aldehydes can result in the formation of the corresponding alcohol
or of 1,2-diols as a result of radical coupling. The amine mediated photo-
reduction of aryl ketones in N-heterocyclic ionic liquids is reported to give
preferentially benzhydrols rather than the expected benzpinacols.25 The ben-
zydrol:benzpinacol ratio is a function of the reduction potential of the inter-
mediate ketyl radical, the results obtained being consistent with a reaction
mechanism which involves a dark ET between this radical and an a-amino
radical. On the other hand it has been reported that the reductive coupling of
aromatic aldehydes and ketones giving 1,2-diols can be carried out in 2-
propanol using sunlight as the photochemical driving force (Scheme 4).26
Negligible amounts of simple photo-reduction products are formed in this
case. Although the reaction proceeds in high yield in many cases, it is however
less successful for nitrobenzaldehydes, hydroxybenzaldehydes, furfural and
cyclohexanone. In the presence of electron-donor sensitizers such as N,N-
dimethylaniline (DMA) or 1,4-dimethoxynaphthalenes (DMN), b,g-unsatu-
rated aldehydes such as (9) undergo a range of photochemical transformations
which involve oxa-di-p-methane rearrangement (forming (10)), decarbonylat-
ion, and proton transfer (Scheme 5).27 The outcome of the reaction depends on
the electron donor used and the fact that competitive ketyl- and alkene-centred
radical anion formation is possible. The ferrocene-anthraquinone dyad (11),
which has a rigid amide spacer, is typical of structures designed to mimic
natural photosynthetic systems.28 A remarkable 7 106-fold extension in the
lifetime of its charge separated (CS) state (Fcd1– AQd) was obtained in
benzonitrile at 298 K by the addition of Y(OTf)3, which binds strongly to the
AQd unit and in so doing decelerates back electron transfer (BET).
3 Reduction of Nitrogen-containing Compounds
A review of the phototochemistry of N-oxides has appeared and this includes a

section on the photo-induced deoxygenation of heterocyclic N-oxides.29 A
second review deals with the mechanistic aspects of the photochemistry of
bicyclic azoalkanes and considers their photo-reduction by hydrogen donors, a
process for which hydrogen-atom transfer and CT mechanisms have been
suggested.30
Photochemistry, 36, 2007, 133–204 137
Me Me
Me Me
Me Me
CHO
+
(10) 1%
16%, inseparable mixture 8%
Me Me
Me
Me hv Me Me HO
CHO CHO
DMN hv
CHO
DMA
13%
Me Me Me
(9) OH Me
(10) 25%
OH
O
16% 4%
Scheme 5
A number of papers have appeared which deal with mechanistic issues

relating to the reduction of nitrogen-containing compounds. Thus an EPR
study has been carried out on the photo-reduction of nitroso compounds in
suspensions of TiO2 in alcohol.31 Nitrosobenzene, for example, is efficiently
reduced under these conditions, forming exclusively the stable radical (12). This
observation is consistent with the generally accepted mechanism for the photo-
reduction. The photo-reduction by amines of a series of nitrobenzenes with
electron-donating and electron-withdrawing substituents in the 4-position has
also been studied.32 EPR spin-trapping experiments showed that photo-reduc-
tion in the presence of triethylamine (TEA) gave only the a-aminoethyl radical
when an electron-donating group was present. This behaviour is reflected in the
fact that these compounds in the presence of an amine are efficient photo-
initiators of methyl methacrylate polymerization. On the other hand, polymer-
ization in the presence of nitrobenzenes with electron-withdrawing groups was
extremely inefficient, reflecting the fact that a-aminoethyl radicals are not
formed in these cases. The nature of the transients observed in a time-resolved
UV-visible spectroscopic study of the amine-mediated photo-reduction of
dinitroarenes, the ultimate product of which is a nitrosoarene, depends on
whether TEA or a N,N-dialkylaniline is used.33 In the case of the former, the
observed transient is believed to be the radical (13), whereas the use of the latter
involves the formation of (14). The photo-reduction of p-nitroaniline has also
been the subject of an EPR study.34 The pulse radiolysis of 8-bromoadenosine
(15) (Scheme 6) has been studied with a view to providing a molecular basis for
the behaviour of RNA radicals and of biologically important adenosine deriva-
tives.35 It was found that the reaction of hydrated electrons with (15) resulted in
the formation of a C-8 radical which, following rapid hydrogen abstraction,
gave the sugar-based radicals (16) and (17). The C-5 0 radical (16) subsequently
138 Photochemistry, 36, 2007, 133–204
O O
N
Fe H
(11) Y(OTf)3
R
N R1
O2NC6H4
N H
N
O HO O
R = Me, R1= H
(12) R = Et, R1 = Me (14)
(13)
NH2 NH2 NH2

N N HO N
N N N
Br
HO N HO N N
N N N
O O O
(15)
HO OH HO OH HO OH
60%
(16)
NH2
e-(aq) NH2 NH2
N
N N N
N N
HO HO N N
N N N N
O 40% O HO +
O
HO OH HO OH
(17) HO OH
Scheme 6
adds to the adenine unit whereas bond cleavage in the C-2 0 radical (17) releases
adenine.
Many papers are concerned with systems and issues relating specifically to
the phenomenon of PET. There is ongoing interest in phthalimides as electron
acceptors in PET processes, and their photochemistry in this regard has been
reviewed.36 A series of fluorescent dimethoxyphthalimides (18) has been used to
explore the detail of the ET process itself.37 Although strong intramolecular
fluorescence quenching was observed for the thioether and the tertiary amine
derivatives, the glycine derivative was the only carboxylate to demonstrate
strong activity. The nature of PET in the 1,8-naphthalimide-spermine conju-
gate (19) and related systems has also been explored.38 Ground-state aggrega-
tion was observed for (19) and the naphthalimide radical anion, and triplet
species were identified from its transient absorption data. The intramolecular
dimer is believed to play an important role in the intramolecular PET processes
Photochemistry, 36, 2007, 133–204 139
in this system. The importance of short range supramolecular interactions

emerges from a study of PET with carboxylated Ru(II) complexes.39 Thus the
use of the carboxylated ligands (20) or (21) facilitates a supramolecular inter-
action with methyl viologen (MV21), leading to the formation of methyl
viologen radical cation (MVd). The peripheral carboxylate is considered to
define a ‘bubble’ of electrostatically attractive space that allows pre-association
with MV21, providing PET with an entropic advantage. Two suitably disposed
carboxylate groups provide an even more favourable electrostatic environment.
Ruthenium complexes, specifically dipolar ruthenium(III/II) pentaamine-N-
methyl-(4,4 0 -bipyridinium) complexes, in a two-phase (water-benzene) system
in which they are soluble only in the water, constitute the first example of a
light-driven molecular switch which is activated by selective irradiation of the
water and benzene layers at 254 and 528 nm, respectively.40 The easily synthe-
sized 5-(2-pyridyl) pyrazolate boron complexes (22) may have potential uses in
organic light emitting devices as they exhibit dual fluorescence in solution as a
result of a PET from the phenyl group to the pyrazolate ligand.41 The photo-
physical properties of a molecular conjugate formed by including a highly
fluorescent acceptor guest (23) in an electron-donating macrocyclic host (24)
has been investigated.42 The crown ether sits loosely at the end of the ant-
hradiisoquinolinium polycycle, and there is evidence that a 3-pseudorotaxane is
formed, based on an interaction with two crown ethers, as the mole fraction of
the former is increased. Photochemically the interesting feature of this system is
that the triplet excited state localized on the polycyclic guest has an energy
which is much lower than the CT state formed by intra-complex PET. This
means that charge recombination populates the triplet state of the guest with
much higher probability than in the absence of complexation.
O
MeO X O
O
N n H
MeO N N
N N
O H
(18) X = SMe, n = 2 O
X = NEt2, n = 1 O
(19)
X = CO2H, n = 1-3, 5
COO
N N N (21)
(20) N
CO2 N N
140 Photochemistry, 36, 2007, 133–204
R
R1
N N N
B (22)
Ph Ph
R1 = CF3, CF3CF2, Ph, But; R = H
R1 = CF3; R = Me
O O O
O O
Me N N Me (24)
PF6- PF6-
O O
(23) O O O
A number of new sensor systems based on PET processes in which nitrogen-

containing units are the acceptors have been described. The 1,3-bisisothio-
uronium-naphthalene conjugate (25) operates on the basis of PET from the
naphthalene to the electron deficient isothiouronium unit.43 The most notewor-
thy feature of this anion sensing system is that, although it forms a 2:1 host-guest
complex with HPO42, binding with acetate involves biphasic 1:1 and 1:2 host-
guest stoichiometries. This suggests that the binding modes of (25) vary accord-
ing to the shape of the oxoanions involved, a feature that could be exploited in
developing fluorescent sensors. Donor-acceptor interactions in the naphthalene-
diiminopyridine ligands (26) are promoted44 by complexation with Zn21. Thus,
although the free ligands do not generate donor-acceptor adducts, the formation
of light-emitting CT species is promoted by metal ion coordination. This effect is
due not only to the fact that complexation results in the creation of an electron
deficient pyridine ring, but also to the geometry imposed on the ligand in the
complex, which favours intracomplex donor-acceptor interactions. Such an effect
could again be of importance in the design of sensor systems.
Me
Ph S NH
R R
N
NH
N N
H H
N N
Me
S
(25) (26) R = H, Me
Ph
Photochemistry, 36, 2007, 133–204 141
O R3 O R2
R3
MeCN, aq NaOH
NH R1 N
hv R1
R2
O O
R 1 = R 2 = R 3= H Yield: 59-90% (based on
R1 = Me, R2 = R3= H 73-92% alkene conversion)
R1 = R2 = Ph, R3= H
R1 = R2 = H, R3= OMe
R1 = Me, R2 = H, R3= OMe
Scheme 7
There continues to be an interest in the development of novel reaction

environments for photochemical reactions. The potential of ‘quasi-solids’, which
are obtained from polysaccharides and contain a lot of water, has been ex-
plored45 using the ET quenching of photoexcited Ru(bpy)321 by MV21. In
agarose quasi-solids, the PET occurs by a dynamic mechanism identical to that
operating in water. PET quenching in anionic k-carrageenan quasi-solid, how-
ever, involved not only a dynamic mechanism but also a static mechanism that
does not require the reaction components to move at all. A microreactor, based
on SiO2 capillaries (length, 5 cm; ID, 530 and 200 mm), to whose inner wall TiO2
coated colloidal SiO2 particles are bound, has been described.46 The reduction of
methylene blue was carried out by injecting a solution of the reactant through the
microcapillary using a syringe pump, while irradiating at 254 nm. A 150-fold
increase in the reduction rate was obtained relative to a comparable batch
system. The photo-reduction by silver nanoparticles of 4-nitrobenzenethiol in
self-assembled monolayers on a gold surface has been reported.47 The reduction
is initiated by visible light (514.5 nm, Ar1 laser) and involves the emission of
photoelectrons by silver nanoparticles in contact with the organic monolayer.
There have been two papers relating to the synthetic application of the
photo-reduction of nitrogen-containing compounds. One of these deals with
the photoaddition of phthalimides to unactivated doubles bonds such as those
in cyclohexene or styrenes.48 The reaction is regioselective in the case of the
styrenes (Scheme 7), giving N-phenylethylphthalimides that are effectively
protected phenethylamines. The reaction involves phthalimide in equilibrium
with its conjugate base, and it is proposed that it proceeds via the nucleophilic
attack of phthalimide anion on the alkene radical cation produced by SET to
excited phthalimide. The N-phenethylphthalimides (27) and (28) were prepared
by the reaction of phthalimide with isosafrole and indene, respectively. The
electron-acceptor properties of the phthalimide group is the key element in a
novel synthesis of cyclic peptides (Scheme 8).49 The acyclic substrates contain
N-terminal phthalimides as the light absorbing electron acceptor and C-termi-
nal a-amidosilane or a-amidocarboxylate groups. Following initial SET to the
excited phthalimide, a series of intra-chain SETs generates a set of equilibrating
zwitterionic biradicals. The conversion of one of these intermediates to a
neutral biradical is the product determining step, with the loss of an
142 Photochemistry, 36, 2007, 133–204
O
O O
O
N N
Me
O O
(27) 51%, 71% conversion (28) 90%, 75% conversion
O
O R R
O R R O N
HO R
N N hv N O
N N E n
SET
R O R R N
O N R
n O
O R
Scheme 8
electrofugal group from a carbon centre next to a radical cation site being an
ideal control process. Recombination of the resulting biradical gives the cyclic
peptide in modest to good yield.
4 Miscellaneous Reductions
A small number of papers dealing with matters of general mechanistic interest

in the context of photo-reduction have appeared. Benzyne radical cations have
been produced using the photo-induced reaction of complexes derived from
fluorine substituted benzenes and Mgd1 (Scheme 9).50 The complexes con-
sidered divide themselves into two groups: those that involve o-difluoro sub-
stituted benzenes and bidentate coordination, such as (29), and those in which
the Mgd1 can only coordinate to one fluorine atom, for example (30). On
photolysis, the former were found to generate benzyne radical cations efficiently
(Scheme 9), whereas yields of the radical cation from the latter were low. It is
believed that the formation of oxetanes by nucleotide bases constitutes an
important route for photo-induced DNA damage and that the photosensitized
cleavage of oxetanes is a correspondingly important repair mechanism. In this
context, the dimethyluracil adducts (31) were synthesized and a study of the
photosensitized cycloreversion carried out (Scheme 10).51 It was shown that the
F
Me Me Me
F hv
Mg + MgF2
F F
Mg
(29) (30)
Scheme 9
Photochemistry, 36, 2007, 133–204 143
O O
R
Me R O Me
N hv, λ > 290nm N O R = H, R1 = Ph
+ R1 R = H, R1 = H
Ph R1
O N hv, photosensitizer O N R = Me, R1 = Ph
H Ph
Me Me
(31)
Scheme 10
cleavage process was consistent with the involvement of oxetane radical anions,
providing further support for the ET repair mechanism. Much of the other
work in this area also relates to PET processes. The PET reactions of organo-
silicon compounds, particularly monosilanes, have been reviewed.52 Particular
consideration is given to the mechanistic aspects of these reactions in which the
organosilanes act as electron-donors. The first definitive evidence that PET
occurs in fluorescein derivatives has been obtained for systems such as (32) in
which the electron-donor aromatic unit is directly attached to the acceptor
xanthene unit.53 Laser flash photolysis experiments produced transient absorp-
tion spectra showing bands due to the radical cation of the aromatic unit and
the radical anion of xanthene. The fluorescence properties of the fluorescein
probes considered were shown to be dependent on the rate of PET from the
aromatic donor to the singlet excited state of the xanthene. It is suggested that
this work provides a quantitative basis for the rational design of fluorescence
probes. Intramolecular PET has been demonstrated for a donor-acceptor
system based on ferrocene attached to a single-wall carbon nanotube
(SWNT).54 The photoexcitation of the SWNT-ferrocene combination with
visible light results in PET and the formation of a long-lived (SWNTd)-
(ferrocened1) species, as indicated by steady-state electrolysis and time-resolved
pulse radiolysis. The general behaviour of these nanohybrids suggests that they
have a promising future in terms of solar energy conversion.
(32)
CO2Me
MeO O O
A number of light promoted reductions are of interest from the synthetic

perspective. The irradiation with a xenon laser of a DMF solution of electro-
generated nickel(I) salen, water and a primary alkyl halide such as 1-bromo-
hexane, followed by a brief exposure to air, results in the formation a product
mixture containing a significant amount of aldehyde (Scheme 11).55 A more
144 Photochemistry, 36, 2007, 133–204
Me H
Ni(I) salen, n-C16H34 +
H2O, O2 42% 33% O
Me Br
DMF, hv n-C8H18 Me
+ +
5% 1%
Scheme 11
Me O
Me
Me
O X
Me O
O O X
X 2 O Me
(33), X = Cl; Yield (X = H, 88%) (34), X = SePh; Yield (X = H, 84%) O
Me
(35), X = OTs; Yield (X = H, 77%)
O
Cl CO (50 atm), SmI2
68%
THF, >400 nm
Scheme 12
Me Me Me Me
LiAlH4
+ +
Me Et2O Me Me Me Me Me Me
O hv OH OH
OH
Me Me Me
Me Me 21% 7%
68%
(36)
Scheme 13
complicated mixture, which contains some 2-octanone, is obtained from 2-

bromooctane. Although the details of the mechanism are unclear, the product
composition is clearly typical of a process involving alkyl radicals. Irradiation
with visible light also has a profound effect on the ability of samarium diiodide
to reduce organic halides and chalcogenides, for example (33)–(35), to hydro-
carbons.56 Carbonylation occurs if the photo-reduction of alkyl chlorides (RCl)
is carried out under an atmosphere of CO (Scheme 12). It is suggested that the
reaction involves the formation of acylsamarium intermediates (RC(O)SmI2)
which dimerize and give the observed products following reduction with further
SmI2. A combination of UV irradiation and LiAlH4 was used to carry out the
reductive cleavage of the allylic ether unit in (36) (Scheme 13), a key interme-
diate in the synthesis of jungianols.57 The reaction involves the photochemical
electrocyclic ring opening of the oxacyclohexa-1,3-diene and reduction with
Photochemistry, 36, 2007, 133–204 145
H H Me
Br t
H
liq. NH3, BuOH
+ +
hv
X X O
X = O, NR CO2Et 91-100% 3-7%

(37)
Scheme 14
Me
ET (37)
+
X hv X X
(38) CO2Et
Scheme 15
O O O
TEA, LiClO4
H H + Me H
MeCN, hv (254 nm)
(39) 40% 3%
Scheme 16
O
O
TEA, LiClO 4
MeCN, hv (254 nm)
(40) 74%
Scheme 17
LiAlH4 of the resulting dienone. A photochemical method for the tin-free

reductive cyclization of suitably substituted aryl halides and the hydrodehal-
ogenation of aryl and alkyl halides has also been reported (Scheme 14).58 The
key feature of the method is that the hydrogen donor is the monoanion (37)
obtained from ethyl benzoate. PET generates the radical anion of the substrate
that fragments to give the radical (38); cyclization and hydrogen transfer from
the benzoate anion completes the formation of the product (Scheme 15). Under
the same conditions, bromoadamantane gives adamantane in 70% yield.
Finally, reductive PET-induced fragmentation of bicyclo[n.3.0]alkanones, fol-
lowed by cyclization, has been used to prepare a new triquinane (39) (Scheme
16) and a new propellane (40) (Scheme 17).59
146 Photochemistry, 36, 2007, 133–204
5 Singlet Oxygen
5.1 Singlet Oxygen. – Most of the recently published work dealing with the
generation of singlet oxygen (1O2) in general, or the design and synthesis of
new photosensitizers in particular, is related to the topic of photodynamic
therapy (PDT). Transient grating measurements have been proposed as a
method for evaluating Type II PDT agents on the grounds that no additional
chemical agent has to be added to the dye solution and that it is sensitive
enough to be used on a micromolar scale.60 The method was applied to a
series of sensitizers, including the recently introduced phthalocyanine (41),
which share a common aromatic macrocycle and metal centre and differ only
in terms of peripherally attached groups. The importance of fluorination on
the properties of dyes is underlined by results obtained for the polyfluorinated
cyanine dye (42), which has been synthesized as a potential fluorescent label.61
The dye exhibited significantly reduced aggregation in aqueous media, an
enhanced fluorescence quantum yield and a greater resistance to photobleach-
ing through direct irradiation or reaction with 1O2. Quantum yields for 1O2
generation by the squarylium cyanine dyes (43) have been reported.62 The
values obtained for a number of the dyes, coupled with the fact that they
absorb in the so-called ‘phototherapeutic window’ (600–1000 nm), has led to
the suggestion that they may be of value as PDT sensitizers. The direct time-
resolved spectroscopic observation of 1O2 phosphorescence has been used to
provide time constants for its population and depopulation, and a measure of
photosensitizer phosphorescence lifetime.63 The behaviour of meso-tetra-
phenylporphine was considered and it was shown that the lifetime of 1O2
decreases with increasing photosensitizer concentration, confirming that it
can also act as a quencher of 1O2. The potential of using ceramic-based
nanoparticles as carriers of photosensitizers for PDT has been described.64
Thus the anticancer drug 2-devinyl-2-(1-hexyloxyethyl)pyropheophorbide
(44) has been encapsulated in the non-polar core of micelles by hydrolysis
of triethoxyvinylsilane. The resulting particles are uniform in size, having an
average diameter of 30 nm, and are stable in an aqueous medium. The uptake
of the nanoparticles by tumour cells, and significant cell death following 1O2
generating irradiation at 650 nm, has been demonstrated in vitro. A number of
new photosensitizers have been developed specifically with PDT in mind.
A series of octaalkynyl tetra-6,7-quinoxalinoporphyrazines have been syn-
thesized and their efficiency in generating 1O2 has been assessed using a 1,3-
diphenylisobenzofuran assay.65,66 The compound (45) was found to be
particularly efficient, generating 1O2 with a quantum yield (0.7) that exceeds
those of some sensitizers currently in use in PDT. The number of carboxylic
acid groups on the water-soluble core-modified porphyrins (46; X ¼ S) had
little effect on the quantum yields for 1O2 generation (F ¼ 0.74–0.80).67 The
corresponding Se analogues were less efficient (F ¼ 0.30). An in vitro study of
the dark and phototoxicities, cellular uptake and localization of these
Photochemistry, 36, 2007, 133–204 147
photosensitizers was also carried out. The production of 1O2 by the sugar-
pendant C60 derivatives (47), obtained together with the corresponding
bis-sugar derivatives from carbohydrate-linked azides, has been demonstrated
by the direct observation of 1O2 emission at 1270 nm.68 The photocytotoxicity
of the mono-sugar derivatives is a function of the pendant sugar unit. A 1:1
complex of lanthanum ion with hypocrellin A (48) combines high efficiency (F
¼ 0.9) for 1O2 generation with a large absorption in the therapeutic window
and high water solubility, and is thus another promising sensitizer in terms of
PDT.69 Finally, the efficient nuclease activity of a ternary copper(II) complex,
[Cu(phen)(met)(MeOH][ClO4], has been attributed to the intercalating prop-
erties of the 1,10-phenanthroline, coupled to the ability of the L-methionine
to generate 1O2 on irradiation with UV (312 nm) or visible light (436, 532
nm).70 It is suggested that the complex will be of value as a PDT agent as it
possesses the bio-essential components copper and L-methionine.
(F3C)2FC CF(CF3)2
F F
F N N F
N
(F3C)2FC CF(CF3)2
N Zn N
(F3C)2FC CF(CF3)2
N N N
F F
F F
(F3C)2FC CF(CF3)2
(41)
O
F F F X X
F
F EtSO4 F N N
S S R O R
F N F
N (43) X = S; R = Me, Et, n-C6H13
Et Et X = Se; R = Me, Et, n-C6H13
(42) X = HC=CH; R = Me, Et, n-C6H13
148 Photochemistry, 36, 2007, 133–204
R R
N N
O(CH2)5CH3
Me Me
Me
NH N N N
Me N
R N N R
N Zn N
N HN
Me Me R N N
N N R
N
t
O Bu
C O2H
(44) (45) R =
N N
t
Bu
R R
R1 R4
sugar
C60 N
X (47)
Sugar: OH OH
N N HO O
O
HO HO
HO O HO
OH
X HO OH O
O O
HO
HO O HO O
R2 R3 OH OH
(46) OH
O
1 2 3 4 HO
R = OCH2CO2H, R = R = R = H; X = S HO OH
R1 = R4 = OCH2CO2H, R2 = R4 = H; X = S HO
O
O
R1 = R3 = R4= OCH2CO2H, R2 = H; X = S HO
OH
O
R1 = R2 = R3 = R4 = OCH2CO2H; X = S
R1 = R4 = H, R2 = R3 = OCH2CO2H; X = Se
O OH
OMe
MeO Me
MeO OH
COMe
OMe
O OH
(48)
Photochemistry, 36, 2007, 133–204 149
A number of papers relating to the generation of 1O2 in a more general context

have also appeared. The incorporation of C60 into a Y zeolite or an MCM-41
silicate framework, for example, results in the significant lengthening of its
triplet-state lifetime such that it persists for several minutes.71 The system is also
capable of generating 1O2 efficiently, as indicated by the detection of a near-IR
emission at 1270 nm. The generation of 1O2 via the triplet metal-ligand CT
(MLCT) states of Ru(II) and Os(II) bipyridyl complexes has been reported, the
efficiencies varying between 0.10 and 0.72.72 The factors affecting these values
include the oxidation potential of the complex, the energy of its lowest excited
state and the spin-orbit coupling constant of the central metal. The potential of
another complex, Pt(binap)2, as a photosensitizer has also been explored, again
using the established 1O2 scavenger, 1,3-diphenylisobenzofufan.73
Finally, there have been a number of mechanistic contributions relating to
the generation and behaviour of 1O2 in a variety of situations. A detailed study
on the effect of solvent on the quantum yield for 1O2 generation by fluoren-9-
one has been reported.74 The quantum yield for intersystem crossing (ISC)
decreases as the polarity and protic character of the solvent increases, resulting
in a corresponding reduction in the quantum yield for 1O2 generation. Quan-
tum yields of unity were observed in alkanes. Although the main agents in TiO2
photocatalysis are hydroxyl and superoxide radicals (O2d), there have been
reports suggesting that 1O2 may also be involved. The generation of 1O2 in an
aqueous photocatalytic TiO2 system has now been demonstrated by the
observation of near-IR phosphorescence at 1270 nm.75 It is suggested that
the most plausible route for its formation is the photocatalytic oxidation of
O2d at the TiO2 surface. The possible role of 1O2 in photocatalysis is discussed.
5.2 Oxidation of Aliphatic Compounds. – A review of the photooxygenation of

1,3-dienes that includes a discussion of its mechanism and applications, and of
the diastereoselectivity of the [4þ2] cycloaddition reaction with 1O2, has
appeared.76 A number of papers have provided additional information about
the mechanism of these oxidation reactions. A kinetic comparison of the
reaction of 1O2 with unfunctionalized alkenes with prenol-type allylic alcohols,
ethers and acetates provides evidence that a combination of hydrogen-bonding
interactions and physical quenching controls the reactivity, regioselectivity and
diastereoselectivity of the ene reaction (Scheme 18).77 The photochemistry of
the retinoid A1E (49) reflects a competition between cyclization, giving
pyridinium terpenoids (50), and peroxide formation, with the outcome being
determined by the concentration of A1E and oxygen, and the lifetime of 1O2, in
the solvent used (Scheme 19).78 A series of physical measurements supports the
involvement of 1O2 in the formation of the cyclic peroxide (51) with, it is
proposed, the A1E acting as a sensitizer.
There continues to be considerable interest in the effect of the reaction
medium on the outcome of 1O2 oxidations. The photo-oxidation of hydrocar-
bons in cation-exchanged zeolites has been the subject of a review in which the
authors focus on their work in this area and assess the industrial potential of
these reactions.79 The examples provided in another review emphasize that the
150 Photochemistry, 36, 2007, 133–204
OH Me OH OH
1
O2
+
Me Me Me Me Me Me
OOH OOH
d.r.
CCl4 93 : 7
CH3OH 73 : 27
CD3OD 68 : 32
> 95 80 82
HO MeO AcO
Me Me Me Me Me Me
d.r. 93 : 7 d.r. 72 : 28 d.r. 40:60
krrel = 1.0 krrel = 0.25 krrel = 0.09
Scheme 18
Me
OH
Me Me Me N
X
Me (49)
hv (λ > 400 nm) hv (λ > 400 nm) Me

MeOH CCl4, O2
OH
H Me Me Me N
Me Me N
OH O
X O (51)
Me Me
(50)
Scheme 19
OOH
HOO
O2, hv Me Me Me Me
Me Me
+
C60, C60-Al2O3 Me
Me
or C60-SiO2 1:1
Scheme 20
reaction cavities of zeolites provide a confined reaction environment that is

well-defined and capable of delivering a high level of selectivity.80 The regio-
selectivity obtained for the 1O2 oxidation of alkenes in zeolite Y due to alkali
metal cation-olefin interactions is one of the examples discussed. Very active
photocatalysts for the liquid phase oxidation of alkenes have been prepared by
depositing C60 on silica and alumina, the use of the latter resulting in a
somewhat more efficient catalyst.81 The oxidation of 2-methyl-2-heptene was
used as a model reaction (Scheme 20), and an approximately one hundred-fold
Photochemistry, 36, 2007, 133–204 151
increase in photocatalytic activity was observed for the supported photosensi-

tizer relative to unsupported fullerene. The same reaction selectivity was
obtained with the supported and unsupported form of the photocatalyst. The
platinum(II) terpyridyl acetylide complex (52) was incorporated into Nafion
membranes and was used as a photosensitizer to promote the photo-oxidation
of 7-dehydrocholesterol, a-pinene and cyclopentadiene.82 It was found initially
that reaction in deuteriomethanol was much more efficient than in methanol,
owing to the much shorter lifetime of 1O2 in the deuteriated solvent. Using a
small amount of D2O to swell the complex-incorporated Nafion membrane
prior to its use in standard undeuteriated solvents produced a highly efficient
photosensitizer that could be recovered and reused 20 times without a signif-
icant loss in efficiency.
N ClO4
MeO N Pt
(52)
Finally, there have been a number of papers that deal with the synthetic
potential of the photo-oxidation of aliphatic substrates. The photooxygenation
of trans-8-(acetyloxy)bicyclo[4.2.0]octa-2,4-dien-7-yl acetate (53) (Scheme 21),
for example, is a key step in the stereospecific synthesis of a new inositol
analogue (54).83 The same group has also used photooxygenation in two
different routes to the cyclohexenetriol (55), which was subsequently converted
to another highly oxygenated system, ()-proto-quercitol (56).84 One route
involves the conversion of cyclohexa-1,4-diene to a mixture of bicyclic endo-
peroxides (Scheme 22) and the other the formation of the epoxy-hydroperoxide
(57a) from cyclohexene epoxide. The 1O2 cleavage of a vinyl ether giving an
aldehyde has been used in the synthesis of tetrazoylacroleins (Scheme 23).85 An
interesting difference in the reactions of cyclopropylidenecyclobutenes (58a)
and cyclopropylidenecyclobutanes (59a) with 1O2 has been reported (Scheme
24).86 The former were found to react slowly, via a photoinitiated, radical
based, autoxidative epoxidation process, forming spiroketones. The
cyclopropylidenecyclobutanes on the other hand react rapidly with 1O2,
OH
H H H
OAc 1 OAc HO OH
O2, TPP, hv
O
CCl4, rt, 70% O
OAc OAc HO OH
H H H
HO
(53) (54)
Scheme 21
152 Photochemistry, 36, 2007, 133–204
OH OH
HO
OH HO OH
OH OH
(55) (56)
OOH OOH OOH

TPP, O2
O O
O + O
hv
12 : 88
Scheme 22
OOH
TPP, O2
O 90%
hv
O
(57a)
OHC
N N
N N N N
N N
MeO
O2, TPP
70%
hv, 4-7 days
CH2Cl2
Cl Cl
Scheme 23
O
R1 R1 O R1
sens, O2
hv
R R R
(58a)
O
HOO
sens, O2 OH
hv
R R R
(59a)
Scheme 24
Photochemistry, 36, 2007, 133–204 153
generating a cyclopropyl hydroperoxide which then undergoes a Hock cleav-

age. It is suggested that the low reactivity of the cyclobutenes may be due to the
fact that reaction would lead to the formation of a cyclobutadiene.
5.3 Oxidation of Aromatic Compounds. – Most contributions relating to the

1
O2 oxidation of aromatic compounds in the period covered by this review are
mechanistic in nature. In work directed towards providing a better under-
standing of the genotoxic, carcinogenic and mutagenic effects of 1O2, the
reaction of 2 0 -deoxyguanosine in the presence of methylene blue under aerobic
conditions has been investigated (Scheme 25).87 The formation of the novel
diimino-imidazole (57) is proposed on the basis of spectroscopic and chroma-
tographic data. It was also shown that (57) is produced directly and that 8-oxo-
7,8-dihydro-2 0 -deoxyguanosine is not involved in its formation. The reaction of
1
O2 with indolizines (58) has been shown to follow a general pattern that
involves initial attack at C-3, forming a peroxidic zwitterionic intermediate (59)
(Scheme 26).88 In methanol this intermediate is trapped giving 3-(2-
pyridinyl)propenoates (60), whereas in acetonitrile the dioxetane (61) in
equilibrium with (59) undergoes homolysis forming a 3-(2-pyridinyl)-2-oxirane-
carboxaldehyde (62). A study of the effect of substituents on the conversion of
O H
HN N
N
NH NH
HO methylene HO N
N HN
N NH2 blue O other
O +
hv, O2 products
OH OH
(57)
Scheme 25
Ar
COAr COAr COAr HO
O
Ph MeOH
Ph Ph + O
N N N N
CO2Me Ph
(58) O OH
R R R R
(60)
1
O2
COAr COAr ArOC

O
Ph MeCN
Ph
N N O N Ph
O CHO
O O
R R R
(59) (61) (62)
Scheme 26
154 Photochemistry, 36, 2007, 133–204
Me
Ar O
Me S H
O O
(63)
Me
HOO N O
Me Me
Me
Me OH Me
Me N HOO N O
TPP, O2 major product
N Me
Me OH
CH2Cl2 Me +
O Me
Me Me
O
HOO N O
Me
Me
50%, 5:1
Scheme 27
4-substituted thioanisoles to the corresponding sulfoxides provides evidence for

an electrophilic mechanism as the rate correlates with s (r ¼ 1.97) and Eox.89
In methanol, sulfoxides are formed via a persulfoxide intermediate, which is
stabilized by the alcohol through hydrogen bonding, nucleophilic addition or a
combination of both hydrogen bonding and nucleophile stabilization (63). The
reaction is slow in aprotic solvent but quickens significantly if carboxylic acids
are added, the protonated persulfoxide being formed in this case.
A few examples of the use of 1O2 as a selective reagent in synthesis have been
reported. Chiral bicyclic lactams have been prepared using a route in which the
diastereoselective oxidative cyclization of 2-methylpyrrole derivatives using 1O2
is the key step (Scheme 27).90 The trans isomers are the major products in all
cases. Considerable selectivity is also displayed in the use of 1O2 as part of a
sequence that discriminates between the two indole units in (64) and completes
the first enantioselective total synthesis of the heptacyclic bisindole alkaloid
okaramine N (65).91 Stable endoperoxides are formed on photooxygenation of
3-alkylidenedihydrofuran-2,4-diones (66) in the presence of CuSO4, with the
reaction involving an initial [4þ2] cycloaddition of 1O2 to the enolic form of the
dione (Scheme 28).92 In contrast, photooxygenation using O2 and tert-butyl
hydroperoxide leads to the formation of hydroperoxides, which slowly decom-
pose to diols. Finally, the use of a photoxidation-reduction sequence has been
used to convert prenylated dihydroxycoumarins and trihydroxyxanthones to
the corresponding o-(2-hydroxy-3-methylbut-3-enyl)phenol derivatives in
yields of 8-65% (Scheme 29).93 The distribution of the photooxygenation
products is controlled by the so-called ‘large group’ effect and a stabilizing
effect due to the phenol groups.
Photochemistry, 36, 2007, 133–204 155
Me Me
N Me Me
Me OH Me OH
N N
i) MTAD
H H H
N H (ii) O2, sunlamp N N
O Me H H
methylene blue O O O
O N O O
H N H H
(iii) Me2S O N N
N
N
H
N Me N N Me
H Me Me Me H Me
(64) (65)
Me Me
Me Me Me
Me Me
Me OOH
O
O2, hv O2, hv
O O O O OH
O CuSO4 TBHP
OH O O
O p-TsOH CH2Cl2
CH2Cl2
n n
n
60 - 67% (66) 60 -72%
Scheme 28
Me O HO Me O HO R
R
Me (i) 1O2 Me
(ii) PPh3 HO O O
HO O O
HO
Me Me
Me
Me O OH Me
O OH
Me (i) 1O2
OH
(ii) PPh3 O OH
O OH
OH OH
Scheme 29
6 Other Oxidation Methods

6.1 Oxidation of Aliphatic Compounds. – In volume terms, the use of TiO2 for
the photodegradation, and ultimately photomineralization, of a wide variety of
substances continues to dominate this area of photochemistry. Although many
of the publications resulting from this work involve the standard application of
156 Photochemistry, 36, 2007, 133–204
the technology to particular chemical systems, the following examples are of

more general interest. The use of photoelectrochemical methods to study
photocatalytic oxidation processes at surfaces such as TiO2 enjoys a number
of advantages, including the fact that the half-reactions occur in different places
rather than on the same particle, as would be the case with colloidal suspen-
sions. A photoelectrochemical study of the photo-oxidation of glucose, an
effective photo-hole scavenger, has been carried out using nanoporous TiO2
electrodes with a view to studying the effect of potential bias, light intensity,
and the concentration of the hole scavenger on the kinetics of the photocat-
alytic oxidation process.94 A model for the overall photocatalytic oxidation
process was proposed on the basis of the results obtained. Extending the
excitation wavelength into the visible is a common theme in relation to TiO2
systems. One way this can be achieved is through surface sensitization which
involves excitation of the sensitizer followed by ET to the semiconductor
surface, the primary oxidizing agent under these conditions being O2d. The
ESR spectrum of O2d on the surface of TiO2 nanoclusters sensitized by the
anisyltritolylporphyrin (67) has now been detected directly for the first time at
room temperature.95 An alternative approach to producing visible light active
TiO2 based catalysts involves their nitridation96. The TiO2xNx photocatalysts
are formed by the direct nitridation of anatase TiO2 nanostructures with
alkylammonium salts, and can be tuned to absorb across the visible region.
It is reported that the activity of the catalysts in promoting the photodegrada-
tion of methylene blue is better than that of commercially available TiO2
catalysts or those produced by other doping procedures. It was also found that
although nitridation at the nanoscale was facile, little or none occurred with
larger TiO2 particles. The diffusion of oxidizing species from illuminated areas
of a TiO2 surface to ‘dark’ areas, resulting in the degradation of molecules
anchored in these areas, has been confirmed.97 The authors suggest that their
findings have implications for how the contribution of dark pores in TiO2
particles is viewed and make the suggestion that relatively large, but highly
porous particles may have photocatalytic potential.
A number of papers have considered the relationship between TiO2 and
other photocatalytic systems. In general it is difficult to prevent complete
photodegradation of hydrocarbons on TiO2, and it is in this context that the
use of V2O5-Al2O3 is proposed as an alternative.98 The system is selective in
terms of the liquid-phase oxidation of cyclohexane to cyclohexanol and cyclo-
hexanone, and a high ketone:alcohol ratio (3.8:1) is also observed. In this
context it has also been reported that the TiO2 photocatalysed reaction of
adamantane in the presence of O2 leads to the formation of 1- and 2-adamant-
anol, and adamantanone, with limited degradation but with modest conversion
(Scheme 30).99 The process involves the formation of an adamantyl radical that
can be trapped not only by oxygen but also by electrophilic alkenes. The
reaction of simpler monocyclic hydrocarbons is less successful. A comparative
study of the photocatalytic behaviour of heterogeneous TiO2 and homogeneous
polyoxometalates (POMs) has been carried out.100 Although the two systems
are similar in that they both involve photo-induced CT and feature OH radicals
Photochemistry, 36, 2007, 133–204 157
Me Me
N
H
N N (67)
H
N CO2Me
NH2
Me O
OH
CN
Me OH
Me CN
Me CN
Me CN TiO2, hv
23% 38%
TiO2, Ag+ O2, H2O O
15% conversion 36% conversion O
75%
O
8% 7%
Scheme 30
as the main photo-oxidant, the study identifies a number of crucial differences.

Thus, although the initial photo-oxidation occurs at comparable rates, photo-
mineralization is significantly slower with POMs. Photo-oxidation with TiO2
involves both OH radicals and direct hole transfers, whereas in the case of
POMs the former is the sole effective oxidant. Significant differences also
emerge with reducible substrates where the rate of ET from POM is signif-
icantly slower than the rate of conduction band ET on TiO2. Finally, the study
indicates that surface reactions between substrates and intermediates play a key
role in TiO2 mediated processes, but are obviously not relevant in the context of
a homogeneous system. The potential of POMs as photocatalysts continues to
excite interest. The fact that POM promoted reactions involve the formation of
radicals has led one group to suggest the decatungstate anion, W10O324, as a
reference sensitizer for 1O2 free radical based oxygenations of organic mole-
cules.101 Thus time-resolved and steady-state methods have been used to
compare the photooxygenation of simple compounds, for example 2-methyl-
2-pentene and 2,3-dimethylbutene, using W10O324 and standard 1O2 sensitize-
rs, such as methylene blue and ruthenium complexes. These studies confirm
that W10O324 sensitized oxygenation occurs exclusively by a radical pathway
that differs clearly from both Type I and Type II oxygenations. The W10O324
photosensitized oxidation of p-substituted 1-aryl-1-alkanols has been investi-
gated (Scheme 31).102 The possibility that the rate-determining step could be
either an ET or a hydrogen-atom transfer between the substrate and the
photocatalyst was considered, but it is concluded on the basis of product
158 Photochemistry, 36, 2007, 133–204
O O
OH
hv, W10O324- R H
R
+
O2, MeCN X
X X
X = NO2, CF3, F, H, Me, MeO 97-100% 0-3%

R = Me, tBu 30-47% conversion
Scheme 31
OOH O OH Cl
OH
SiO2/W10O324-
+ + + O + +
hv
Cl
Product MeCN 82.5 10 6 1.5 0 0

Distribution CH2Cl2 24.5 16 8.5 1.5 42.5 1.5
(%)
Scheme 32
analysis and kinetic data that the latter is in fact involved. The same group has
shown that this photooxygenation can also be carried out using DCA as a
photosensitizer.103 In this case product analysis and Hammett correlations
support an ET mechanism. The importance of radicals in POM promoted
reactions is underlined by the use of tetrabutylammonium decatungstate to
generate cycloalkyl radicals from cycloalkanes.104 The radicals react in a
Michael fashion with electron deficient alkenes, giving addition products in
60–65% yield with complete conversion of the alkene. The presence of CH2Cl2
has a significant effect on the photocatalytic oxidation of cyclohexene and
cyclooctene using (Bu4N)4W10O32 supported on silica (Scheme 32).105 The
CH2Cl2 undergoes oxidation, giving radical intermediates that are involved in
the subsequent epoxidation of the alkenes. Although cyclooctene epoxide is
stable under the reaction conditions, cyclohexane epoxide undergoes ring
opening to form 2-chlorocyclohexanol. The photodegradation to CO2 and
F of nonafluoropentanoic acid, a model perfluorinated acid, by H3PW12O40
has been reported.106 The result is significant because the TiO2 mediated
photomineralization of trifluoroacetic acid is not very efficient. The effect of
O2 on the photoisomerization of all-trans-1,6-diphenyl-1,3,5-hexatriene, a
model for long-chain polyenes related to retinal and vitamin A, has been
reported.107 The presence of air enhances the photoisomerization of the termi-
nal alkene unit but reduces that in the centre. Evidence is provided that
excludes the involvement of 1O2 and also the radical cations of the all-trans
material in this new isomerization pathway to the cis,trans,trans isomer. A
mechanism is proposed which involves CT from the S1 state of all-trans
material to O2 followed by collapse of the exciplex to either a zwitterionic or
a biradicaloid species. The process is completed by rotation about the new
single bond in this intermediate followed by reversion to the triene and O2.
Photochemistry, 36, 2007, 133–204 159
The synthetic applications of the photo-oxidation of aliphatic systems

include the formation of 1,4-monoprotected dialdehydes, 1,4-ketoaldehydes,
g-lactols and g-lactones by means of the radical alkylation of a,b-unsaturated
aldehydes in organic and organic-aqueous media (Scheme 33).108 The key step
in the process is the generation of radicals from 1,3-dioxolanes or alcohols by
photomediated hydrogen abstraction using benzophenone in an organic sol-
vent, or benzophenone disodium disulfonate in water. These radicals then add
to the a,b-unsaturated aldehyde. The outcome of the oxidative fragmentation
of the norcholestanyl acetate (68) using Pb(OAc)4 depends on whether the
reaction is carried out thermally or photochemically (Scheme 34).109 The latter
results in a mixture of products, effectively formed via the radical intermediate
(69), in which nor-secosteroidal ketones predominate. The reaction with
Pb(OAc)4 under thermal conditions results in the stereoselective formation of
O R R3 OH
R1 R2 CHO R3 O OH
O O H R4 H
R4
CHO Ar2CO, hv Ar2CO, hv
R1 R2
O R water or MeOH water or MeOH R1 R2
Scheme 33
H Me H
Me H
Me C8H17 H H
H +
AcO
AcO O
Me H O
Pb(OAc)4 11% 16%
H H
hv
AcO H Me H
OH
(68)
+ H + O H
Pb(OAc)4, ∆ AcO AcO
O OAc
22% (A) 8%
Me H
(A) 65% H
+ O H
+ O H
AcO
17% AcO
22%
Me H
H
AcO
O
(69)
Scheme 34
160 Photochemistry, 36, 2007, 133–204
5,10-ethers with a b-oriented epoxy bridge. It is suggested that cationic inter-

mediates may be involved in this case. The potential of alkyl aryl ketones as
delivery systems for the controlled release of fragrances has also been con-
sidered.110 The required precursors can be readily synthesized and on irradi-
ation in undegassed solvent with a xenon lamp or using sunlight undergo a
standard Norrish Type II reaction, releasing the perfumery alkenes. GC-MS
analysis of the irradiated solutions allowed a number of by-products, which
had not been previously detected in such reactions, to be characterized. The
majority of these are formed via the intermediate (70) that results from the
reaction of the standard 1,4-biradical with O2. The 7,9-dimethylcyclohe-
pta[b]pyrimido[5,4–d]furan-8(7H),10(9H)-dionylium ion (71) and its S-ana-
logue (72) are isoelectronic with the 5-ethyl-3-methyllumiflavinium ion (73).
This relationship to flavin systems provides the rationale for mechanistic
studies designed to provide further insight into the role played by these
cofactors in biological redox reactions.111,112 These ions have been prepared
as their tetrafluoroborates and it has been shown that they participate on
irradiation in the autorecycling oxidation of alcohols under aerobic conditions
(Scheme 35). Evidence is provided that the process involves ET from excited
(71) or (72) to the alcohols.
ET is also involved in a range of other processes of synthetic interest, a
number of which centre on ring-opening reactions of small strained ring
systems. In addition to its synthetic potential the oxidative cycloreversion of
oxetanes is of biological importance as it is involved in the enzymatic repair of
O R
O
HO
X
(70)
Me Me
X Me N N O
N
O
+
+ N
N Me N Me
Me
O Et O
(71) X = O (73)
(72) X = S
OH O
(71) 12%, based on alcohol consumed

hv, MeCN 311%, based on (71)
Scheme 35
Photochemistry, 36, 2007, 133–204 161
UV damaged DNA. The ET-mediated cycloreversion of trans,trans-2,3-diphe-

nyl-4-methyloxetane has been found to be photosensitizer dependent (Scheme
36).113 The reaction involves cleavage of the C2–C3 bond in the oxetane radical
cation and the formation of the trans-b-methylstyrene radical cation when
chloranil is used as a sensitizer. In the case of pyrylium salts, the trans-stilbene
radical cation, formed via O–C2 bond cleavage in the oxetane radical cation, is
involved. Radical cation and diradical intermediates have been simultaneously
observed for the first time, using a variety of spectroscopic techniques, in the
PET-initiated degenerate rearrangement of the methylenecyclopropane (73)
(Scheme 37), for which a radical-cation cleavage, diradical cyclization,
mechanism has been proposed.114 Nanosecond time-resolved absorption spec-
troscopy on laser flash photolysis of (73) with, for example, 9,10-di-
cyanoanthracene (DCA) identifies two transients, which have been assigned
to the trimethylenemethane radical cation (74) and the corresponding diradical
(75). The same group has obtained evidence that the related rearrangement of
the 2-methylenecyclobutanone (76) involves the intermediate (77), a novel oxa
analogue of the tetramethyleneethane radical cation (Scheme 38).115 The for-
mation of the 2-silacyclobuta[2.3]cyclophane (78) and its cycloreversion take
Me
O Ph Ph
pyrylium +
+ MeCHO +
salts Ph
Me Ph Ph Ph
hv
O
chloranil
Ph Ph Me
hv O Ph Ph
PhCHO + +
+ Me Me
Ph Ph
Scheme 36
Ar Ar
Ar Ar Ar Ar
D D
D
(74) D D
D
DCA
DCA BET hv
hv
Ar Ar Ar Ar Ar Ar
D
D D
D
D
(
(73) ((75) D
Scheme 37
162 Photochemistry, 36, 2007, 133–204
Me Me
Me Me
Me Me
chloranil
Ar hv Ar Ar
O O O
Ar Ar
Ar
(76) (77)
Scheme 38
Me
Si sens
sens Me hv
hv
Me Me
(78) Si
Si
Me Me
(78)
Me
Si
Me
(79)
sensitizer = p-dicyanobenzene/phenanthrene
Scheme 39
t
Bu Me
t
Ar Bu DCA, hv Ar OR
. . + ROH .
Ar Me MeCN, 12 h Ar H
Ar = Ph, p-ClC6H4 R = Me, Et, Pr 26 - 60%
(80)
Scheme 40
place under PET conditions (Scheme 39).116 The quantum yield for the cyclo-
reversion is greater than one, leading to the suggestion that a chain mechanism,
in which the key step is ET between the open-form radical cation (79) and (78),
is in operation. Finally, the photoaddition of alcohols to a 1,2,3-butatriene type
cumulene (80) in the presence of a catalytic amount of DCA has been reported
(Scheme 40).117 The reaction is regioselective and involves the formation of the
cumulene radical cation as an intermediate. The design and construction of
PET systems designed to mimic photosynthesis continues to be a very active
research area. An example of such a system is the carotene (C)-porphyrin (P)-
fullerene (C60) triad (81) for which a Cd1–P–C60d CS state with a lifetime of
340 ns and a dipole moment of greater than 150 D has been reported.118
Photochemistry, 36, 2007, 133–204 163
C60
N
n
Bu Me Me
n N
Bu H Me
N N
Me H n
Bu
N
(81)
H
N
Me Me Me Me Me n
Bu
O
Me Me
Me
6.2 Oxidation of Aromatic Compounds. – As was the case for aliphatic

compounds, the use of TiO2 based systems and other so-called ‘advanced
oxidation technologies’ (AOTs) dominate this area of photochemistry. The
examples that follow are some of the more interesting recent contributions in
this research field. The effect of ozone on the photocatalytic oxidation of
toluene, chosen as a model VOC, was considered in a comparative study that
included the use of O3-UV, TiO2-UV and O3-TiO2-UV in a flow reactor.119 It
was concluded that the O3-TiO2-UV system was the most efficient, as photo-
catalyst deactivation was not a problem and residual O3 concentration was low.
As the use of UV light is required with standard TiO2 systems, many contri-
butions in this area are concerned with the development of photo-oxidation
systems that are activated by visible light. Thus it is reported that S-doped TiO2
photocatalysts absorb visible light (l 4 440 nm) strongly and display high
activity for methylene blue degradation.120 A range of metal-ion based photo-
catalysts have also been developed for the degradation of organic pollutants.
These include copper phthalocyaninesulfonate, which was found to be effective
in aerated aqueous solution for the visible light (l 4 450 nm) degradation of 4-
chlorophenol, 2,4-dichlorophenol, 2,4,6-tri-chlorphenol and methyl orange.121
The novel b-cyclodextrin-hemin complex (82) has been used at neutral pH and
at l 4 450 nm to activate hydrogen peroxide for the oxidation and mineral-
ization of 2,4-dichlorophenol and rhodamine B.122 The photocatalyst com-
bined high activity with high turnover numbers and excellent stability. Another
group has looked for an explanation for the effect of visible light on the rate of
oxidation of chlorinated phenols, including 2,4,6-trichlorophenols, by hydro-
gen peroxide in the presence or absence of iron catalysts.123 They conclude that
the photo-acceleration is due to the formation of the light-sensitive 2,6-di-
chloro-1,4-dibenzoquinone (83), whose photochemical conversion to 2,6-di-
chlorohydroquinone and 3,5-dichloro-1,2,4-benzenetriol completes the early
phase of the oxidation process (Scheme 41). The ability to utilize visible or
near-UV light is one of the attractions of POMs in terms of photo-oxidation.
The sulfo-polyoxometalate anion clusters S2W18O624, S2Mo18O624,
and SMo12O402, for example, have been used together with a 7 W lamp
164 Photochemistry, 36, 2007, 133–204
Me Me
N N
Fe Cl
N N
Me Me
O O
O O
(82)
OH O OH OH
Cl Cl Cl Cl Cl Cl Cl Cl
H2O2 H 2O
+
catalyst hv
HO
Cl O OH OH
(83)
Scheme 41
(312-700 nm) to photo-oxidize benzyl alcohol, ethanol, and (–)-menthol.124

Although oxidation of the reduced form of the tungsten POM occurs in the
presence of H1 or O2, this method of closing the catalytic cycle is not feasible
for molybdenum clusters. The oxidation of the reduced forms of all three
POMs, however, may be achieved, or accelerated, by working in the presence of
an electrode held at a potential more positive than the first redox potential of
the POM anion. A sunlight promoted procedure based on these POMs, and
involving particularly simple reaction conditions, has been developed by the
same group for the selective oxidation of benzyl alcohol.125
The use of a variety of surface-modified TiO2 photocatalysts has been
described. The effect of fluorination has been explored in terms of the behav-
iour of four model compounds – phenol, acid orange 7, and sodium di- and
trichloroacetate – chosen because their photodegradation mechanisms are quite
different.126 It was found that the fluorinated TiO2 was more effective than pure
TiO2 for the photocatalytic oxidation of phenol and acid orange 7, but less so
for dichloroacetate. It is concluded that OH radical mediated oxidation path-
ways are enhanced on the fluorinated surface, whereas hole-transfer mediated
oxidations become less effective owing to the hindered adsorption of substrates.
The reductive dechlorination of trichloroacetate is less efficient on the fluori-
nated surface, a fact that is attributed to the high electronegativity of the
Photochemistry, 36, 2007, 133–204 165
h+ h+
Ar Ar
hv
O Ar Ar
TiO2 Ar
O
Ar
Ar Ar
Ar Ar
Scheme 42
fluorine in surface Ti–F species, which reduces interfacial ET rates. The

TiO2-WO3 system has generated a lot of interest in terms of its photo-electro-
chemistry. It has been reported that the ability of TiO2 to promote the photo-
oxidation of acetaldehyde in the gas phase and of 2-naphthol in the liquid phase
is considerably reduced when it is coupled with WO3, an effect attributed to a
decrease in the rate of ET from the semiconductor to O2.127 When the electrons
are removed electrochemically from a WO3 film with a SnO2 underlayer,
however, the photocatalytic activity for the oxidation of 2-napththol exceeds
that of TiO2. A number of other papers have appeared which underline the
importance of TiO2 based photocatalysis. The possibility of a cascade hole
transfer from TiO2 to a free alkene via adsorbed p-phenylbenzoic acid has been
demonstrated using time-resolved diffuse reflectance spectroscopy (Scheme
42).128 It is suggested that a cascade process such as this has synthetic potential.
A key element in the operation of a dye-sensitized solar cell is that BET to the
radical cation of the dye should be as slow as possible. It has now been shown
that the modification of the surface of TiO2 nanoparticles with sodium dodecyl
benzyl sulfonate significantly reduces the rate of BET.129 The results relate to a
femtosecond transient absorption spectroscopy study of alizarin-sensitized
surface-modified and unmodified TiO2 nanoparticles. It is suggested that the
energy of the Fermi level of the nanoparticles increases on surface modification,
thus raising the overall free energy of reaction for the BET process.
The selective photo-oxidation of aromatic substrates has been the focus of
attention for a number of groups. Although photocatalysis using TiO2 gener-
ally results in the significant photodegradation of organic compounds, it can
result in more selective oxidation in certain cases. Thus the TiO2 catalysed
photooxygenation of electron-rich 1,1-diarylethenes and 1,1,8,8-tetraaryl-1,7-
octadienes gives 1,2-dioxanes in high yield (Scheme 43).130,131 It is also reported
that the PET process is significantly accelerated by the addition of MgClO4.
Evidence has been obtained for the involvement of epoxide and aldehyde
intermediates in the zeolite-promoted oxidation of 1,1-diarylethenes, and this
has led to the formulation of a detailed mechanism for these reactions (Scheme
44).132 Evidence was also obtained that the aldehyde intermediates undergo a
novel photooxygenation in competition with a-cleavage. Zeolites also feature in
another selective photo-oxidation system which involves iron(II) pipyridine
166 Photochemistry, 36, 2007, 133–204
hv ( λ > 280 nm)

Ar Ar Ar
O2
TiO2, Mg(ClO4)2 Ar Ar
Ar O O
MeCN
hv ( λ > 280 nm)

Ar Ar O2 H H
Ar Ar
Ar Ar TiO2, Mg(ClO4)2
MeCN Ar Ar
O O
Scheme 43
O2
Ar O O
hv hv
Ar Ar2CH Ar2CH + CHO
Ar H
Ar
hv
O O Ar O Ar2CH2 + CO
O Ar2CH O2
Ar Ar H
Ar
∆, hv
- H 2O
O O
Ar2CHOOH Ar2CH Ar2CH O2
OOH
H
Scheme 44
Me2N NMe2 Cl
O O
Fe(bipyr), O2
+
hv (visible)
H 2O Me2N Me2N NMe2
major minor
Scheme 45
supported on NaY zeolite and demonstrates excellent reactivity without lead-

ing to extensive photodegradation (Scheme 45).133 The oxidation of aromatic
groups with O2 in the presence of N-bromosuccinimide (NBS) has been
reported (Scheme 46).134 It is suggested that the reaction involves hydrogen
abstraction from the aromatic methyl by a photochemically generated bromine
atom and the subsequent reaction of the benzylic radical with oxygen. The
photocatalysed oxidation of an aromatic methyl to the aldehyde level, in
systems containing both electron-withdrawing (CN) and electron-donating
Photochemistry, 36, 2007, 133–204 167
Me CO2H
NBS (1eq), hv
EtOAC
X X
t
X = H, p- Bu, p-OMe 32-85%
p-CN, p-Ph, p-NO2
m-OMe
Scheme 46
CN Ph
Me CHO Me CHO
F F
O2, O2,
F F N
CN Me
CN hv, λ > 300nm CN Me hv, visible light Me
Scheme 47
N N
Sc(OTf)3 Sc(OTf)3
N N
Me Me Me
Me Me Me Me Me CH2OH
O2
hv radical
Me Me Me Me chain Me Me
Me Me Me
Scheme 48
(Me) groups, has been described.135 The appropriate choice of photocatalyst

allows a high level of selectivity to be achieved in these reactions (Scheme 47).
The key step in this reaction is PET from the aromatic system to the singlet
excited state of the photocatalyst. The visible light driven conversion of
a-methylstyrene to acetophenone has been carried out in the same way using
10-acridinium perchlorate as photosensitizer.136 The same group has also
discovered that Sc(OTf)3 has a significant promotional effect on PET in
photooxygenation reactions of this type (Scheme 48).137 The effect is not only
apparent with acridine, which can form a complex with Sc(OTf)3 in the ground
state, but also with pyrene, for which no such interaction occurs. No photo-
oxidation is observed in the absence of Sc(OTf)3.
The mechanism of the photohydroxylation of 1,4-benzoquinone in water,
which results in the formation of equal amounts of 2-hydroxy-1,4-benzoqui-
none and hydroquinone, has been re-examined.138 The quantum yield and laser
168 Photochemistry, 36, 2007, 133–204
O O O OH OH
OH
H 2O
+
O O O O O
(84)
O
H 2O
OH
O
H
OH O
OH
OH
OH
OH
Scheme 49
flash photolysis data obtained are explained in terms of a rapid equilibrium

between monomeric excited benzoquinone and an exciplex (84) (Scheme 49).
Product formation can occur through addition of water to the monomeric
benzoquinone to give an adduct which is immediately oxidized by benzoqui-
none or which prior to this oxidation undergoes rearrangement to a trihydroxy
benzene. Alternatively, the exciplex (84) can undergo ET and water addition,
again ultimately forming 2-hydroxy-1,4-benzoquinone and hydroquinone. The
mechanism thus discounts any suggestion that the photohydroxylation involves
hydroxyl radicals. The visible light initiated photochemistry of riboflavin in the
presence of 3- or 7-hydroxyflavone has been investigated, in part because the
processes involved may operate in nature.139 The triplet state of riboflavin is
generated in solutions containing mM or sub-mM concentrations of the
flavones, which quench the excited state through an ET process. The reaction
of the semireduced riboflavin thus formed with dissolved O2 produces O2d,
which in turn reacts with riboflavin or 3-hydroxyflavone. No evidence was
found for the involvement of 1O2 or the reaction of 7-hydroxyflavone with
O2d. The photochemistry of flavothione (85), and a number of hydro-
xyflavothiones, in ethanol has been described.140 The primary photochemical
process for flavothione is hydrogen abstraction from the solvent to give a
radical that in the absence of O2 forms dimers; in the presence of O2 the major
product is flavone (Scheme 50). This reaction involves ground-state O2 rather
than 1O2. The behaviour of the hydroxyflavothiones depends on the substi-
tution pattern and ultimately on the ordering of the excited states. Both 6- and
7-hydroxyflavothione, and 7,8-dihydroxyflavothione, which like flavothione
itself have lowest (n,p*)3 states, produce the parent flavone and dimers. The
hydroxyflavothiones with lowest (p,p*)3 states – 3,6- and 3,7-dihydroxy-, and
Photochemistry, 36, 2007, 133–204 169
O Ph O Ph
(85) H H +
O Ph O Ph Ph O Ph O
EtOH
hv O2
hv O Ph
S SH
(85)
Scheme 50
3-hydroxyflavothione – act as photosensitizers, producing 1O2, which then

reacts with the ground state of the flavothione. Pterins, which also occur in a
wide variety of biological systems, are also light sensitive. The photo-oxidation
of 6-(hydroxymethyl)pterin (86) in alkaline aqueous solutions, the only product
of which is 6-formylpterin, has been investigated.141 The data obtained are
consistent with the formation of an intermediate (87) in an O2-independent,
photochemical process and its rapid conversion to 6-formylpterin in a reaction
that also produces one equivalent of hydrogen peroxide. Although 6-(hydro-
xymethyl)pterin (86) is a relatively good sensitizer for 1O2 formation (F ¼ 0.21),
this active oxygen species is not involved in the conversion of 6-(hydroxyme-
thyl)pterin (86) to 6-formylpterin.
O O O O O
O2 H2O2
N CH2OH H CH
N N CH
N hv N N
H 2N N N H 2N N N H 2N N N
H
(86) (87)
PET is the key feature of many other photo-oxidations involving aromatic

substrates. It has been shown, for example, that pyrene and anthracene which
are covalently attached to silica, gold or indium-doped tin oxide (ITO),
undergo a photo-oxidation forming dihydroxy/dione derivatives.142 The reac-
tion involves O2d, formed by ET between excited pyrene, or anthracene, and
O2, and it is suggested that the implications of such a photodegradation need to
be considered when polycyclic aromatic hydrocarbons (PAHs) are used as
spectroscopic probes in surface adlayers. The redox photosensitized amination
of 1,2-benzo-1,3-cycloalkadienes, arylcyclopropanes, and quadricyclane with
ammonia and primary amines, using 1,2,4-triphenylbenzene (1,2,4-TPB) or
2,2 0 -methylenedioxy-1,1 0 -binaphthalene in the presence of m- or p-dicyano-
benzene (DCB), has been described (Scheme 51).143 The process involves the
formation of the radical cation of 1,2,4-TPB, for example, by PET to the DCB,
followed by hole transfer from the radical cation to the substrate, the latter
170 Photochemistry, 36, 2007, 133–204
1,2,4-TPB
1 m-DCB NHR2
R 2
+ R NH2
MeCN-H2O R1
1 hv
R = H, Me R 1 = R2 = H 79%
R1 = Me, R2 = H 83%
R1 = H, R 2 = iPr 52%
1,2,4-TPB NH2
m-DCB
+ NH3 71%
Ph Ph MeCN-H2O Ph Ph
hv, Et4NBF4
Scheme 51
R R
R Ph
Ph Ph Me
Ph
hv Ph Me hv
Ph
DCA DCA
Me Ph Ph
Ph Ph Ph
Ph
(88) R = H, Me
Scheme 52
being the key step. The PET-induced rearrangement of the bicyclopropenyls

(88) gives both benzene and Dewar benzene derivatives in product ratios that
depend on the irradiation time (Scheme 52).144 These experimental results
indicate that the PET-promoted bicyclopropenyl-benzene rearrangement oc-
curs via a Dewar benzene intermediate, and as similar mechanisms have been
proposed for the Ag1 catalysed and thermolytic rearrangement of bicyclopro-
penyls, they suggest that all three routes share a common structural pathway.
The PET promoted isomerization of hexamethyl Dewar benzene to hexame-
thylbenzene using cyanonaphthalenes as electron acceptors has been the subject
of a kinetic study which addresses the importance of the reorganization energy
involved in the BET in the radical cation-radical anion exciplexes.145 A differ-
ent diastereoselectivity is obtained for the [2þ2] cycloaddition of stillbene to a
chiral fumarate if selective excitation of the CT complex is employed rather
than direct excitation of the substrate (Scheme 53).146 Reflecting the fact that
the structures of the excited CT complex and the normal exciplex are different,
the diastereomeric excess (de) of the product and its temperature profile depend
on the manner of excitation. The product de increases with increasing temper-
ature, and the chirality of the product is also temperature dependent. Overall,
the approach provides another method of controlling the stereoselectivity of
photochemical reactions. Quantum yield data have been used to show that the
photochemical Diels-Alder reaction of anthracenes, such as 9,10-dime-
thylanthracene (DMA), with fumaronitrile and p-benzoquinone proceeds via
Photochemistry, 36, 2007, 133–204 171
Ph CO2R Ph CO2R
hv, 313 nm
+ exciplex
Ph RO2C direct
Ph CO2R
+
Ph
CO2R
CT hv, 366 nm excited CT
complex CT complex complex CO2R
excitation Ph
Scheme 53
O O
O Me O
H
DMA1 O Me
H
Me
O
O Me O Me
Me
Scheme 54
Me
Me Me Me
Me Me
Me
Me PET
1,4-dicyano-
tetramethylbenzene Me
Me H2O, - H+
Me
Me Me
Me Me Me
Me
Me - e, -H+
or - H HO
HO
Me
Me
Scheme 55
ET from the singlet excited state of the anthracene to the dieneophiles.147

Subsequent cation-anion coupling gives a diradical which closes to give the
cycloadduct (Scheme 54). Spectroscopic evidence – a transient absorption
spectrum at 298K for the radical ion pair and ESR data at 77 K for the
diradical – is provided in support of the proposed mechanism. A biomimetic
photochemical cascade cyclization process has been developed for the synthesis
of aromatic polycyclic terpenoids.148 The regioselective and stereoselective
reaction involves a PET produced radical cation, which is trapped by water,
leaving a radical which initiates a cascade cyclization leading to an all-chair
polycyclic structure (Scheme 55).
172 Photochemistry, 36, 2007, 133–204
Finally, a series of donor-acceptor PET systems have been reported in which

the donor is a aromatic system. The anthracene-fluorescein-C60 triad (89) and a
related structure have been synthesized.149 The anthracene, acting as an ‘energy
antenna’, collects light in the 320–400 nm range and transfers it to the ‘reaction
centre’, the fluorescein. The fluorescein, following absorption of light in the
visible region, is involved in the generation of a CS state through PET to C60.
Coordination of a Ru(II) terpyridyl metallo-fragment to the terpyridine unit in
(90) results in the appearance of a weak phosphorescence at 710 nm, which is
attributed to MLCT, or to an intra-ligand CT from pyrene to the coordinated
terpyridine unit.150 It is suggested that the system, because of the position of the
luminescence maximum, the long emission lifetime, and the possibility of using
the thiophene as an anchor through appropriate functionalization, may have
potential as a bio-marker. Both PET (k E 6.2 109 s1) and energy transfer
(k E 6.2 109 s1) processes have been identified in a pyrene-perylene bisimide
dyad (91) using time-resolved emission and femtosecond transient absorption
spectroscopy.151 Temperature-dependent time-resolved emission spectroscopy
provides evidence that the dyad can exist in two conformations – folded and
stretched – that have different barriers to ET. The potential of this system in
constructing metallo-supramolecular structures through the coordination of
metal ions to the pyridine units has been highlighted.
PET
COO(CH2)2OOC
C60
COO(CH2)2O O O
N
Me energy
(89) transfer
N
S
N
Et
(90)
Photochemistry, 36, 2007, 133–204 173
O O
O O
O O
N N
O O
O O
O O
(91)
The spectroscopy and dynamics of a dyad in which the donor and acceptor
are linked by a spacer – the heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14]tetrade-
cane system – that is characterized by high symmetry, rigidity and linearity
have been reported.152 The importance of the alignment of the p-orbitals of the
donor and acceptor is underlined by the data obtained for (92) and (93), which
show that the rate of PET in the former is significantly greater (3.9 1010 s1)
than in the latter (7.0 108 s1). Remarkably, the ET state of the 9-mesityl-10-
methylacridinium ion (94) has a lifetime (2 h at 203 K) which is much longer
than that of the CS state of the natural photosynthetic centre which can extend
to several seconds.153 Its energy (2.37 eV) is also significantly larger than that
that of the natural system (0.50 eV). These features result from the fact that the
ET state of (94) is formed through a single-step PET and because of the
minimal reorganization energy of the system. The dyad (95), based on eosin
and tris(2,2 0 -bipyridine)Ru(II), acts as an efficient photosensitizer for reactions
such as the photooxygenation of anthracene.154 The active oxygen species is
O2d, generated by ET from the CS state of (95), which is generated by PET.
The photosensitization ability of (95) and its broad absorption range in the
visible region suggest that it should have applications in many situations
involving ET. The photophysics and photochemistry of benzyl derivatives of
isoquinoline N-oxides (96) have been studied.155 The only products formed on
irradiation were the parent amine and a product resulting from an intramo-
lecular hydroxylation (Scheme 56). A two-step rather than a concerted mech-
anism is preferred for the reaction. The reaction involves hydroxyl radicals,
formed by N–O bond scission in the radical cation produced through PET from
the benzene ring to the isoquinoline acceptor. The regioselectivity of
174 Photochemistry, 36, 2007, 133–204
subsequent C–O bond formation is controlled by the electron distribution of

the radical cation.
CN CN
S S
CN CN
S S
(92) (93)
Me Me
Me Me Me Me
hv
N N
Me Me
(94)
2
O
O N
Br Br N N
Ru 2ClO4-
NaO O O N N
Br Br N
(95)
O
N N N
R R R
R hv, λ > 300 nm
R + R
CH2Cl2, TFA
R HO
R R
R R R R R R R
R R
(96)
Scheme 56
Photochemistry, 36, 2007, 133–204 175
7 Oxidation of Nitrogen-containing Systems
Arising from the facility with which many nitrogen-containing systems can
donate an electron, there have been many reports relating to the photo-
oxidation of nitrogen-containing systems. Much of the work in this area
focuses on donor-acceptor systems which are of importance in the context of
artificial photosynthesis or as photosensors.
A number of contributions which are not specifically related to PET are
broadly synthetic in scope. A number of papers have appeared which describe
the synthesis of indolocarbazoles, substances which possess a wide range of
biological activities, and use a photochemical cyclization as the key step. Thus
the preparation of indolo[2,3-a]pyrrolo[3,4-c]carbazoles via the I2 promoted
oxidative photocyclization of bisindolylmaleimides has been reported (Scheme
57).156 A second group has prepared indolocarbazoles using the same method,
or using acetone as the effective oxidizing agent (Scheme 58).157 In the case of
the 2-naphthyl derivative (97), the regioselectivity of the two methods is quite
different. This group has also developed a route to the same indolocarbazoles
which is based on a Heck cyclization. A comparison of the photochemical and
the palladium-catalysed routes indicates that, although lower yields are ob-
tained with the latter, it does not require high dilution conditions and involves
shorter reaction times. Another oxidative photocyclization, in this case involv-
ing the formation of a C–N bond, is involved in the preparation of the stable
heteroaromatic cation (99) (Scheme 59).158 The reaction proceeds faster when
I2, or a mixture of I2 and AgClO4, is included in the reaction mixture. The
H H
N N
O O O O
hv, I2 R R
R R
THF-MeCN
R R 3-24 h, 84-90% R R
N N N N
H H H H
Scheme 57
H H H
N N N
O O O O O O
hv
+
N N N
H H H
(97)
benzene, I2 : 74%, 100 : 25
acetone: 73%, 100 : 0
Scheme 58
176 Photochemistry, 36, 2007, 133–204
Me Me
Me
Me Me
Me
hv, O2
R N R N R
N
H
R OH- R
R
(98) (99)
O
O
R = R = OMe R=R= O
O
O
Scheme 59
O O O
NOH NaOMe, MeOH
OH OMe
+
Me hv, rose Bengal
Me Me Me
1: 2.8, 92%
O O O
1
O2 O O NO
N O O O
R R R
N O
R1 R1 R1
O O O O O
esters MeOH
acids R1
R R1 R
O
(100)
Scheme 60
crown ether derivative (98) forms a complex with Mg21, but in this form
cyclizes more slowly as a result, it is suggested, of hydride removal being less
efficient as a result of complexation.
The photoxygenation of the C ¼ N in a-iminocarbonyl compounds results in
C–C cleavage and the formation of mixtures of acids and esters (Scheme 60).159
The key intermediate in the proposed mechanism is the trioxa[2.1.0]pentane
(100). An autorecyling process is suggested to account for the greater than
100% yields obtained for the oxidation of some amines by 6,9-disubstituted
cyclohepta[b]pyrimido[5,4-d]pyrrole-8(6H),10(9H)-dione derivatives such as
(101).160 A possible mechanism involves an initial PET between (101) and the
amine, followed by the generation of O2d and the regeneration of (101)
(Scheme 61). The actual product isolated is the result of a secondary reaction
between the initially formed imine and excess amine. The related
Photochemistry, 36, 2007, 133–204 177
O2 O2
Bn Bn
NH2
N N
N N
O R1 R2 O NH2
+
N hv N R1 R2
Me Me
O O
(101)
O2
R1
NH2
N R2 R1 R2 NH
NH3
R1 R2 R1 R2
Scheme 61
O O
Me Me
N N
N Me N
O O
N (102) N Bn (103)
H N N
R
NH hv
+ C60
HN degassed C60
toluene
Scheme 62
1,6-methanocycloundeca[b]pyrimido[5,4-d]pyrrole-12,14-dione derivatives (102)

and (103) also participate in the same type of autocycling photo-oxidation of
certain amines and alcohols.161 A photochemical method involving oxidative
dehydrogenation has been used to carry out the mono-addition of substituted
piperazines carrying alkyl, ether, amide and hydroxyl functional groups to C60
(Scheme 62).162 The reactions, which are believed to proceed via radical-ion
pairs formed by ET from the amine to the fullerene, are selective in that they
involve monoaddition and the substituents on the piperazine ring adopt an exo
configuration relative to the surface.
178 Photochemistry, 36, 2007, 133–204
A number of general reviews have appeared that deal with aspects of PET in
systems in which the donor is a nitrogen-containing unit, among them being a
review of the role of metal ions in controlling photochemical and thermal ET
through complexation with radical anions.163 Another review focuses on the a-
heterolytic reactions of aminium radicals which are formed by one-electron
oxidation of amines.164 PET and triplet sensitized di-p-methane rearrange-
ments have been reviewed with particular reference to the aza-di-p-methane
variation of the reaction.165
There have been a number of reports relating largely to the mechanistic
aspects of PET in nitrogen-containing systems. Details of the first examples of 2-
aza-di-p-methane rearrangements have been provided.166 Specifically it has been
shown that 2-aza-1,4-dienes undergo a triplet sensitized rearrangement, with
(104), for example, giving a vinylaziridine (105) and a cyclopropylamine (106)
which results from the SiO2 promoted hydrolysis of an initially formed imine
(Scheme 63). Of greater importance is the finding that these rearrangements also
take place under SET photosensitized conditions, with (104) giving again the
vinylaziridine (105) and in addition a new cyclopropylamine (107) (Scheme 64).
Ph Ph Ph Ph Ph Ph
sensitizer
N (104) + Ph + H N
hv N
Ph Ph Ph Ph
Ph
SiO2 SiO2 Ph Ph Ph
(104)
(105)
Ph Ph Ph Ph 3%
NH2 Ph
NH2
Ph Ph
Ph
83% (106) 11%
Scheme 63
Ph Ph Ph Ph Ph Ph Ph
DCA, biphenyl Ph
N N + N
N
MeCN, hv Ph
Ph Ph Ph Ph Ph Ph
Ph Ph Ph Ph
Ph
(104) (108) (110)
(109)
Ph Ph Ph
Ph Ph Ph Ph
Ph
H N Ph SiO2 Ph
N H H
Ph Ph Ph NH2 N
Ph Ph
Ph Ph Ph
Ph
(105) 11% (107) 19%
Scheme 64
Photochemistry, 36, 2007, 133–204 179
In this case, the SET generated radical cation (108) can produce (105) via an
aziridinyl radical cation (109), or (107), via the radical cation (110) formed by
phenyl migration. Fluorescence quenching in the fluorescein derivative (111) is
possible because of a conformational equilibrium which involves the linking
methylene group between the electron-donor and fluorescein adopting an axial
position, thus allowing the aniline nitrogen to approach the fluorescein unit.167
The fluorescence quantum yield for (111) is thus only 20% of that for 2 0 ,7 0 -
dichlorofluorescein. The quantum yield for (112) is even lower, at 3.6% of the
fluorescein value, providing evidence of cooperative quenching by the two
aniline nitrogens. This conclusion is reinforced by the increase in fluorescence
intensity that occurs when b-cyclodextrin is added to a solution of (112), a fact
that is attributed to one of the aniline nitrogens being unable to participate in
quenching due to complexation with the cyclodextrin.
CO2H CO2H
Cl Cl Cl Cl
O O O O
N N N
N N N
(111) C6H4pOMe pMeOC6H4 (112) C6H4pOMe
A number of synthetic applications of PET reactions of N-donor systems have

been reported. A change in the regioselectivity of photoamination of veratrole
(113) with ammonia and amines occurs when the reaction is carried out in the
presence of cyclodextrins.168 The effect is attributed to a change from an SN2Ar*
mechanism in which the nitro group is meta-directing to a mechanism involving
ET which leads to para-substitution. It is suggested that enhanced ET occurs in
the presence of cyclodextrin due to the formation of a veratrole-amine complex
in its cavity. A modest diastereomeric excess was observed for the PET-promoted
cyclization of N-acyl-a-dehydro(1-naphthyl)alanines (Scheme 65).169 The
H NHCOR1 H NHCOR1
O O
O NHR N N
R R
+
1
NHCOR
O R
MeOH/MeCN (1:9) NHCOR1
TEA, hv NHR
N
O
R = (S)- CH(Me)CO2Me; R1 = Me R1
+ +
Conversion: 63%; de = 55%
Scheme 65
180 Photochemistry, 36, 2007, 133–204
NO2 NO2 NO2
MeNH2
+
hv
OMe NHMe OMe
OMe OMe NHMe
(113) THF/H2O (1 : 9) 9.5 : 1
γ -CD, MeOH/H O (1 : 1) 1 : 15
2
Me
+
Me Me Me
HN
33%
N
+
hv
5%
C6H6 or MeCN
HN 10% HN
(114)
Scheme 66
R R H R
N N
HN Nu
hv NuH
HN HN
R R
HN
R = H, Me NuH = MeOH, Et2NH
R
Scheme 67
diasteoselectivity is attributed to hydrogen-bonding control of the enolization

step that completes the formation of the 3,4-dihydrobenzo[f]quinolinone. The
conversion of the stilbenylpyrrole (114) to a mixture of an indole and an
isoindole is initiated by an intramolecular PET from the pyrrole to the alkene
(Scheme 66).170 Subsequent transfer of the pyrrole N–H to the radical anion
generates two biradicals, closure of which gives the observed products. This is
believed to be the first intramolecular addition of a pyrrole to a stilbene double
bond. The same group has also used this PET, pyrrole N–H transfer and radical
recombination sequence, to convert styryl dipyrroles to unstable 2-[[1-(2H-
pyrrol-2-ylidene)methyl]-2-indanyl]pyrroles which can be trapped by nucleo-
philes giving functionalized indanylpyrroles (Scheme 67).171
Photochemistry, 36, 2007, 133–204 181
An enormous amount of resources and imagination continues to be invested

in the synthesis and study of molecular and supramolecular donor-acceptor
systems designed to mimic photosynthesis. Many of these systems involve
nitrogen-containing molecules, particularly porphyrins, as electron-donors.
Photo-induced energy-transfer processes in fullerenes, currently the most com-
monly used acceptors in these systems, has been reviewed.172 The issues
affecting the competition between energy transfer and ET are given particular
attention. Fullerene-porphyrin systems, the most widely used donor-acceptor
combination, are the subject of a second review which considers a range of
issues including the self-assembly of porphyrin-fullerene monolayers and the
significance of the fact that fullerenes have small reorganization energies.173
The CS state of the zinc imidazoporphyrin-C60 dyad (115) is reported to have a
particularly long lifetime (310 ms) for a donor-acceptor system that involves a
single-step ET.174 The extended lifetime is attributed to the nature of the
linkage, the energy of the CS formed and solvent effects. An exceptionally long-
lived CS state (120 s in frozen benzonitrile at 120 K) is obtained following PET
from the zinc chlorin unit to C60 in the dyad (116).175 The very short donor-
acceptor separation is the key contributing factor in determining the lifetime of
the CS state. The single-step ET process that is involved, again avoids the loss
of energy that is associated with multi-step ET. Up to 15 electrons can be
accommodated in the triply fused diporphyrin-C60 conjugate (117).176 Because
of its low-lying and very short-lived singlet state, however, the photo-induced
process which occurs in (117) is energy transfer from the C60 units rather than
the ET to C60 that occurs in the bisporphyrin analogue.
Ar Ar But
N Me
N N Ar =
N Zn N
N
C60 But
H
N
Ar Ar
(115)
C60
N
Me Me
Et Me
N N
Zn
(116)
N N
Me Me
O N O CO2Me
C6H13
182 Photochemistry, 36, 2007, 133–204
Ar Ar
N N N N
Zn Zn
N N N N
O
O
O O
Ar Ar
O C60 C60 O
(117)
O O
Me Me
The ET dynamics in zinc porphyrin-arene diimide systems with aryl(ethynyl)

spacers, such as (118), have been explored using pump-probe transient absorption
spectroscopy.177 The conjugated nature of the (aryl)ethynyl bridge plays a role in
the charge-recombination reactions of these species by increasing the extent to
which the porphyrin radical cation is delocalized. A series of dyads in which an
imide is connected directly to a zinc porphyrin in the meso postion has been used to
explore the factors affecting the energy gap involved in PET charge separation and
thermal charge recombination.178 The effect of Sc31 and Lu31 complexation on
PET in the zinc porphyrin-naphthalenediimide dyad (119) and a related zinc
porphyrin-pyromellitdiimide-naphthalenediimide triad has been reported.179 The
metal ions bind to the radical anion of the diimide unit and thus have no effect on
the rate of charge separation, as complexation occurs only after PET. The driving
force for the charge-recombination process, however, decreases as the concentra-
tion of the metal ion is increased, suggesting that metal complexation can be used as
a method of controlling BET in appropriate cases. The use of light to control PET
has been achieved by covalently linking a porphyrin to a photochromic di-
hydroindolizine unit.180 Irradiation with UV light generates the ring-opened form
of the photochromic unit and initiates rapid PET to give the CS state (Scheme 68).
Charge recombination occurs in 2.9 ps, generating the ground state. As the ring
opening process can be reversed photochemically or thermally, light can be used to
switch PET on and off. The characteristics of a dyad consisting of two directly
tethered quinoxaline-fused porphyrin systems, one containing Zn(II) and the other
Au(III), have been reported.181 The CS state generated by PET in this dyad,
ZnPQd1-AuPQ, has an exceptionally long lifetime (10 ms) in non-polar solvents,
sufficiently long enough to allow its ESR spectrum to be measured at 143 K.
Ph
O O O O
N N
H17C8 N N C6H4 Zn C6H4 N N C8H17

N N
O O O O
Ph
(118)
Photochemistry, 36, 2007, 133–204 183
O
Tol C6H13
N
O
N N O O
N
Tol Zn N
N N O
(119)
Tol
PET
NC
O O N CN
CN hv, 366 nm N
P N P N
H N hv, 590 nm H
CN ∆
N
Scheme 68
A number of non-porphyrin donor-acceptor systems have also been de-

scribed. Thus a comparison of azulene-C60 and naphthalene-C60 dyads, on the
basis of flash photolysis experiments, shows that azulene is a better donor, even
though both it and naphthalene have a 10p-electron system.182 The synthesis
and properties of a series of semi-rigid donor-(sigma spacer)-acceptor systems
(120) and (121) has been reported.183 PET generates a CS state in all cases, and
with the dicyanovinyl acceptors this undergoes conformational ‘folding’ in non-
polar solvents. The results show that changes can be made in the donor and the
acceptor without changing the basic photophysical properties of the systems.
This has led to the suggestion that these materials are suitable for incorporation
into organized arrays or polymers. PET in the donor-(steroid spacer)-acceptor
dyad (122) occurs184 with FSET ¼ 0.14 and kSET ¼ 1.6 107 s1. The observed
isomerization of the norbornadiene unit to quadricyclane is shown to occur as a
result of triplet-energy transfer and ET, both of which, it is suggested, occur by
a through-bond mechanism. The dynamics involved in PET systems consisting
of an imide acceptor and multiple donor sites has been explored (Scheme 69).185
On the basis of the results obtained it is concluded that if the lowest energy
zwitterionic biradical contains the most reactive radical cation then an efficient
and regioselective reaction will ensue. However if the lowest energy zwitterionic
biradical is the least reactive then the reaction will have a low quantum
efficiency and its outcome will depend on the relative energies of the transition
states for the competing reactions. In other words the Curtin-Hammett
principle applies in these cases.
184 Photochemistry, 36, 2007, 133–204
MeO2
Me R 1 CN
N N
Me R2 CN
(120) MeO2 (121)
R1 = R2 = CN
R1 = CO2Me, R2 = CN
R1 = CO2Me, R2 = CO2Me
R1 = CO2(CH2)11Me, R2 = CO2(CH2)11Me
O
Me OCCH2 N
Me
O
CO
(122)
CO2Me
O O
PET
N Y E N Y E
X hv X
O O
O
Y
HO X
N Y E
N X
O
O
E = SiMe3, CO2NBu4; X =NMe, O, S, NMs; Y = NMs, NAc
Scheme 69
Sub-picosecond photo-induced charge injection from ‘molecular tripods’

into mesoporous TiO2 has been achieved over the distance of 24 Å (Scheme
70).186 The three-point attachment to the TiO2 surface and the rigidity of the
spacer in molecules of such remarkable architecture as (123) facilitate control of
the distance and orientation of the sensitizer with respect to the surface. Details
of PET in two dendrimer system have been reported. The first contains a
perylenediimide as an acceptor core, a rigid second generation polyphenylene
Photochemistry, 36, 2007, 133–204 185
o
24 A
TiO2 O
O
O
TiO2
N 2
Ru(bpy)2
O
N
TiO2
(123)
O
TiO2
O
PET, 240 fs
Scheme 70
skeleton and triphenylamine donors on the outside.187 Dendritic molecules of

this type have been used to demonstrate forward and BET at a single-molecule
level. The second involves dendritic multiporphyrin arrays with a C60 core.188 It
is considered that the actual PET involves the porphyrin directly connected to
the C60 core, but that the energy required is harvested by the porphyrins in the
dendritic antenna. It is also proposed that the PZnd1 generated by the PET at
the core should migrate towards the outside of the dendrimer by means of a
hole-hopping mechanism. Thus overall the porphyrin array not only harvests
light but also retards the BET process. In natural photosynthesis, photosystems
I and II act in concert to achieve significant charge separation. The tetrad (124),
which contains two donor-acceptor pairs, has been designed to explore this
aspect of the natural system.189 The zinc porphyrin and the perylenedicarboxi-
mide can be excited selectively by irradiation at 420 nm and 540 nm, respec-
tively. In both cases, however, the CS states that result undergo rapid charge
recombination, thus corresponding to a zero output by the system. Neverthe-
less, the sequential formation of both CS states on a 50 ps time scale leads to the
central ion pair undergoing charge recombination, leaving the distal ion pair.
This CS state has a lifetime of 650 s. In this way the tetrad (124) demonstrates
AND gate behaviour in analogy to photosystems I and II.
C5H11
R
O O O
N N
N
Me
N Zn N N C8H17
N N
Me N N
O O O
R
R = 3,5-di-t-butylphenoxy
C5H11
(124)
186 Photochemistry, 36, 2007, 133–204
PET also been studied in a number of supramolecular systems. Adamantan-

amine which is known to bind strongly to b-CD has been covalently linked to a
porphyrin via a flexible hydrocarbon chain.190 In aqueous solution, PET between
this porphyrin and mono-6-p-nitrobenzoyl-b-cyclodextrin was found to involve
both free donor and free acceptor, and donor and acceptor bound in a supra-
molecular complex (125). The latter was found to be remarkably fast (kSET E 1
109 s1), being very close to that of a covalently linked porphyrin-nitrobenzene
dyad. Intrarotaxane PET has been reported by two groups. Sauvage type
rotaxanes (126) have been synthesized by a convergent route.191 The topology
of these systems requires that electronic interaction between the porphyrin and
the C60 must occur through the [Cu(phen)2]1 complex. Spectroscopic evidence
was obtained for the (ZnPd1)2-[Cu(phen)2]1-C60d CS state, which had a lifetime
of the order of ms, significantly longer than the value (180 ns) obtained previously
for a structurally related porphyrin-C60 rotaxane held together by hydrogen
bonds.192 A 3-rotaxane consisting of an anionic phenylene ethynylene dumbbell
(127) threaded through two cationic cyclophanes has been synthesized, and its
ability to participate in PET with the acceptors methyl viologen, dipropyl-4,4 0 -
bipyridinium disulfonate, and anthraquinone-2,6-disulfonate has been as-
sessed.193 A Stern-Volmer analysis shows that quenching of the fluorescence of
the dumbbell by PET to the quencher is inhibited by the presence of the threaded
cyclophane. This effect, which is both steric and electrostatic in the case of
cationic quenchers, has led to this rotaxane being described as an ‘insulated
molecular wire’. If a rotaxane is to operate as a molecular machine in which the
threaded unit moves in response to PET mediated changes in the dumbbell, then
it is essential that the lifetime of ET states should be long enough to allow this
movement. It has been established that the lifetime of such states is increased by
several orders of magnitude in the pore of zeolites and related aluminosilicates.
Although attempts to incorporate a rotaxane based on the dumbbell molecule
(128) into the mesopores of Al/MCM-41 were unsuccessful, the dumbbell
molecule (128) was incorporated and the photochemistry of the resulting com-
bination was explored.194 It was found that the 4,4 0 -bipyridinium radical cation
formed by PET was very long lived and that PET occurred between the
aluminosilicate framework and excited units in (128).
NO2
O PET
Ph
O
N N
N (CH2)n Zn Ph
H
N N
(125)
Ph
Photochemistry, 36, 2007, 133–204 187
ZnP
N N
PF6-
Cu+
C60
N N
ZnP
(126)
-
O3S SO3-
(127)
-
O3S SO3-
Me N Me
Me
Me
Me Me N
Me Me N
N
N 2+ N
Ru
N
N N t
Bu
N O
Me Me (128) O
Me
Et
t
Bu
PET involving nitrogen-containing units as donors is the key process under-

pinning the operation of many fluorescence detectors. The application of PET-
modulated fluorescence and luminescence in the context of chemosensors, and
of biosensors which depend on conformationally induced alterations in PET
efficiency, has been reviewed.195 The potential of these systems to deliver single-
molecule sensitivity in relation to monitoring individual binding events in
solution, on surfaces or in polymers is addressed. The boronic acid derivatives
(129) have been evaluated as fluorescent disaccharide sensors,196 their action
depending on a covalent interaction between sensor and substrate. The selec-
tivity of the sensor was a function of the length of the linking methylene chain,
and in general considerable specificity was displayed for disacchadides for
which pyranose-furanose isomerization is possible. A number of new cation
sensors have been described. A series of sensors based on p-phenylenediamine
188 Photochemistry, 36, 2007, 133–204
and dansyl groups as the donor and acceptor units, respectively, have been
synthesized and evaluated in terms of their response to Group I and Group II
cations.197 The sensors (130) and (131) displayed the greatest selectivity
between Mg21/Ca21 and Na1/K1 owing to size considerations and the
charge-density sensitivity of the phenylenediamine moiety. A series of N-aryl-
N 0 -(9-methylanthryl)diaza-18-crown-6 derivatives has also been prepared by
the same group and assessed as photosensors, with (132) showing particular
selectivity for Ca21 in comparison to Mg21, Na1 and K1.198 A 1H NMR study
indicates that the Ca21 induces large downfield shifts of the crown-ether
protons, whereas the other cations have a lesser effect. There is thus a good
correlation between the fluorescence response and the NMR data. The sensor
(133), consisting of 4-amino-1,8-naphthalimide as fluorophore and a structur-
ally simple receptor, demonstrates a remarkable selectivity for Zn21.199 Other
physiologically important divalent cations, such as Ca21 and Mg21, and ions
such as Cu21, Co21, Ni21, Hg21 and Cd21, produce either no fluorescence
enhancement, or only a minor enhancement at high concentration.
OH OH
B B
OH HO
N N
n
Ph
(129) n = 3 - 8
Me
N
O
O Me
N N N SO2
O
O
(130)
Me
N O O
Me
SO2 N N N
O O
(131)
Photochemistry, 36, 2007, 133–204 189
O O
N N
Et
O O O N O
(132)
CO2Na
CO2Na
HN
(133)
The 4-amino-1,8-naphthalimide group has been linked via the same spacer
to an anion receptor, a thiourea, giving (134), systems which function as
combined fluorescent and colorimetric chemosensors.200 On interaction with
anions such as F or AcO the fluorescence of (134) is quenched as a result of
PET, whereas in the presence of large concentrations of F, there is a
pronounced change in the absorption spectrum, where the lmax shifts from
455 to 550 nm. It is suggested that this is the first example of a combined
fluorescent-colorimetric sensor. Two new sensors based on boradiazaindacene
(BODIPY) have been reported. The paramagnetic BODIPY derivatives (135)
are designed to provide information through ESR and fluorescence measure-
ments, as the nitroxide is sensitive to the redox status of the system, and the
fluorescence intensity is decreased if acid or a cation is added due to proto-
nation/chelation of the pyrroline nitrogen atom.201 The bis-BODIPY substi-
tuted bipyridyl zinc complex (136) displays a 25-fold enhancement in
fluorescence intensity in the presence of HPO42.202 A similar enhancement
is displayed by other anions with the exception of sulfate and fluoride. The
effect is due to a simple electrostatic interaction between the complexed Zn21,
and the anion which stops the PET from the BODIPY unit and restores its
bright green fluorescence. The fluorescent chemosensor (137), bearing two
imidazolium groups at the 1,8-position of anthracene, selectively recognizes
the biologically important H2PO4 ion.203 Ab initio calculations suggest that
(137) should bind selectively to H2PO4 ion, in preference to Cl, Br or I
ions, through a ‘tweezer-like’ binding action. In practice, the selectivity shown
by (137) for H2PO4 ion was approximately 200 times that for ions such as
Br or I. Evidence for strong binding of anions to the sensor was also
obtained using 1H NMR spectroscopy. Finally, the use of the resorufin
derivative (138) as a PET sensor involves an entirely different approach.204
Although the natural fluorescence of the phenoxazinone system in (138) is
quenched by PET from the p-nitrophenyl group, the addition of Pb21 ions
leads to the hydrolysis of the phosphate ester bonds and a fluorescence
enhancement which is directly proportional to the concentration of the
Pb21 ions. The system showed good selectivity for Pb21 ions in preference
to a range of alkaline earth and transition metal ions.
190 Photochemistry, 36, 2007, 133–204
Et
O N O
S NH
NH
R = H, CF3 HN (134)
Me
F
O F B
Me Me N
N
Me N
Me Me
n
Me
Me R Me
Me Me Me
N
N N N
Me B Me F Zn2+
F F B N
n = 0, R = H, Me, Br F
N (136)
n = 1, R = H
Me
(135)
Me
Me Me
N N O2N
O
O O O
N N P
O
O
-
N
2PF6
(138)
(137)
8 Miscellaneous Oxidations
There have been a number of contributions relating to photo-oxidations in

which silicon plays a role. The photochemistry of silicon substituted phthalim-
ides has been the subject of a review which discusses how organosilanes can
participate efficiently as donors in PET, with the resulting radical cations
undergoing rapid desilylation, producing radicals that form carbon-carbon
Photochemistry, 36, 2007, 133–204 191
bonds through recombination or addition to unsaturated systems.205 The PET-

promoted formation of the radical cations of silyl enol ethers and their use in
intramolecular reactions has also been reviewed.206 The domino cyclization of
such silyl enol ether radical cations has been used for the construction of steroid
backbones.207 Thus the irradiation of the silyl enol ether (139) (Scheme 71) in
the presence of a catalytic amount of sensitizer results in a domino cyclization
generating five additional stereogenic centres in a single reaction. A further
example of the use of this methodology involves the PET-mediated conversion
of cyclopropyl(vinyl) silyl ethers carrying an olefinic or acetylenic side chain
into bi-, tri-and tetracyclic ring systems via radical and radical cation interme-
diates (Scheme 72).208 Not surprisingly, all the cyclization products feature cis
ring fusions, reflecting what would be the highly strained nature of trans ring
junctions in the polycyclic products.
Me
Me
H
Me
H
H O Me
Me
H Me
Me H
Me DCA, hv (420 nm)
Me
Me + H
H O
OTMS
Me H
(139) Me
H
Me
+ H
H O
26% (47 : 41 : 12)
H
Scheme 71
OTMS O
OTMS
DCN nucleophile
hv (350 nm)
MeCN
O O
H
H H
Scheme 72
192 Photochemistry, 36, 2007, 133–204
R O
hv + R 2S
R2S + O2 R 2S + O2 2 R2SO
sens O
R
(140)
Scheme 73
hv +
1 R 2S O O R2SO
R2S + O2 R 2S + O2
sens
(141)
Scheme 74
A number of groups have reported findings in relation to the photo-

oxidation of sulfides and sulfoxides. The oxidation of aryl methyl sulfoxides
using Ru(III)-polypyridyl complexes, generated photochemically using O2 as
oxidant, has been the subject of a flash-photolysis study.209 The observation
of the absorption spectrum of a transient that could be assigned to a sulfoxide
radical cation confirms ET as the rate determining step in these oxidations.
The relative importance of ET and 1O2 mechanisms in the photooxygenation
of dibutyl sulfide and thioanisole using N-methylquinolinium tetrafluorobo-
rate (NMQ) and DCA has been assessed.210 It has been shown that oxidation
of both sulfides with NMQ involves ET (Scheme 73). Although ET is again
involved in the DCA oxidation of thioanisole, the principal route for oxida-
tion of dibutyl sulfide involves 1O2 (Scheme 74). Evidence is presented which
suggests that a thiadioxirane (140) rather than a persufoxide (141) is involved
in the ET photo-oxidations of sulfides. It has also been reported that aryl
selenides and aryl selenoxides are efficient trapping agents for the intermedi-
ates involved in the reaction of 1O2 with sulfides, the latter trapping the
intermediate persulfoxide (141) and former trapping the S-hydro-
peroxysulfonium ylide (142).211 The process has synthetic potential in the
context of the oxidation of selenides and selenoxides to selenones, as the
photooxygenation of selenides in the presence of 4-5 equivalents of dimethyl
sulfide, or of selenoxides in the presence of 1.5 equivalents of dimethyl sulfide,
leads to the formation of the selenone in greater than 90% yield. This
dye-sensitized photo-oxygenation has also been successfully applied to the
conversion of phosphites to phosphates.212 A PET involving the tetrabutyl-
ammonium salt of (phenylthio)acetic acid plays a role in the formation of
what is believed to be the first example of an ion pair consisting of a
benzophenone radical anion and an organic cation, and of a photo-induced
Hofmann elimination in quaternary ammonium ions (Scheme 75).213 Two
synthetically useful functional group transformations involving sulfur
compounds have been described. A photocatalytic system for the oxidation
of sulfides to sulfoxides, which is based on a heterogeneous nafion membrane
containing a lead ruthenate pyrochlore catalyst and a [Ru(bpy)3]21sensitizer,
has been developed.214 Over-oxidation to the sulfone level is not a problem
with this system, separation of the product is straightforward and the
Photochemistry, 36, 2007, 133–204 193
OH
O
S R1
R
(142)
Me Me
Me Me
N N
Me Me
O O O O
Ph Ph
Me Me
O
O
Ph S S Ph
Ph Ph
Me
Me Me
Me Ph
+ N O + S + CO2
Me N Ph
Ph Ph
OH Me
Me
Ph
Me
Scheme 75
multi-component membrane can be recycled. A yield of 96% was obtained for

the oxidation of p-acetylphenyl methyl sufide. The regeneration of carbonyl
compounds from 1,3-dithianes by means of a photochemical oxidation has
also been described.215 The experimentally simple procedure involves 30%
hydrogen peroxide and proceeds in relatively high yield.
Tetrathiafulvalene (TTF) is an excellent donor in PET processes, and so it
has been incorporated into a number of donor-acceptor systems that have
been constructed in the context of artificial photosynthesis. A series of
supramolecular dyads based on TTF and C60, of which (143) is typical, have
been constructed, the interesting feature being the fact that the donor and
acceptor units are held together through biomimetic hydrogen bonding.216
Through-space ET was confirmed in these systems using transient absorption
spectroscopy, with the lifetime of the CS state being of the order of hundreds
of nanoseconds to microseconds. Picosecond transient absorption spectros-
copy has been used217 to show that PET in the dumbbell triad (144), on which
the ester substituents confer solubility in organic solvents, takes place from
the singlet excited state of C60. The C60-TTFd1-C60d state decays with a
lifetime of 20 ns in benzonitrile. The synthesis of a donor-acceptor dyad (145),
194 Photochemistry, 36, 2007, 133–204
H17C8
O N
NH C60
ET
NH O
S
N
NH O S S
S
(143)
TBDPSO
CO2(CH2CH2O)3CH3
CO2(CH2CH2O)3CH3
S S
C60 C60
S S
H3C(OCH2CH2)3CO2
H3C(OCH2CH2)3CO2
(144)
S S
CH2CO2C(CO2Et)2
C60F15
S S
(145)
C8H17 Me
N
S S
S S C60
MeS H17C8
S S
(146)
S S
Photochemistry, 36, 2007, 133–204 195
O O
SMe
S(CH2)12 N N (CH2)12S S S
MeS S S
O O S S SMe
S S
MeS
(147)
SCH2CH2O
S S
OCH2CH2S
S S
(148)
H13C6 S S
Me Me
H13C6 S S S(CH2)12O
(149)
N O NO2
visible light Me
uv
or heat
featuring an all-trans 18p annulenic fluorofullerene (tranulene) and three

pendant tetrathiafulvalene units, has been described.218 Tranulenes are par-
ticularly attractive light-harvesting units in donor-acceptor assemblies as they
have a strong absorption at 665 nm that allows the CS state to be produced
using visible light. In this case the CS state is energetically low-lying and
relatively long-lived (870 ns). The donor-acceptor dyad (146) involves a C60
unit that is connected to a tetrathienylethylene (TTE) via a quaterthiophene
(4T), both of which could donate electrons to the C60 through PET.219
Nanosecond transient absorption spectra in benzonitrile provides evidence
for the formation of (TTE-4T)d1-C60d, in which the radical cation is delo-
calized over both the TTE and the 4T sub-units. The lifetime of the CS state in
benzonitrile is only 18 ns. A series of triads, including (147), based on TTF
and naphthalenediimide (NIm) building blocks, have been constructed and
the photophysical consequences of varying the spacer units and the end-
groups have been assessed.220 The efficiency of PET, was lower for (147) than
for its analogue in which the flexible methylene chain was replaced by a more
rigid cyclohexyl spacer. Absorption bands at 480 and 760 nm in the nano-
second transient spectra in benzonitrile were attributed to the TTFd1-NImd-
TTF CS state. Similar triads based on a perylenediimide acceptor have also
been synthesized and investigated.221 The reduced fluorescence and
196 Photochemistry, 36, 2007, 133–204
H13C6 S S NO2
Me Me
H13C6 S S S(CH2)12O
(150)
N O
Me
Scheme 76
Me Me
Me Me
PR2
PR2
B R 2P H
R 2P H
H Ru Me Me
Ru
R 2P B
R 2P H
PR2
PR2 Me
Me
(151) (152)
Scheme 77
fluorescence lifetimes observed for these triads relative to N,N 0 -di-

hexylperylenediimide was attributed to PET. The triad (148) has potential
as a redox fluorescence switch, as, although it is only weakly fluorescent as a
result of PET, fluorescence enhancement occurs in the oxidized radical
cationic form.222 Thus sequential electrochemical oxidation and reduction
results in the reversible modulation of its fluorescence. The possibility of using
light to control a redox process – effectively the inverse of what happens with
(148) – has also been demonstrated by the same group.223 The spiropyran unit
in the dyad (149) can be photochemically switched to an open form (150)
(Scheme 76). The addition of Fe31 to a solution of (149) results in ET, the
conversion of the TTF unit to TTFd1 and the formation of Fe21. Subsequent
irradiation produces the open form of the spiropyran to which the Fe31
coordinates, resulting in a significant reduction in its oxidation potential. This
results in ET back to the TTFd1 and so the presence of the spiropyran unit in
(149) facilitates the photochemical control of ET between Fe31 and TTF.
Finally, although ruthenium phosphine hydrides such as (151) do not react
with pinacol borane thermally, they undergo photochemical H–B oxidative
addition to give metal boryl hydride complexes224 (Scheme 77). The major
product (152) has a cis stereochemistry although the trans isomer is also formed
as a minor product.
References
1. H.S. Nalwa (ed.), Handbook of Photochemistry and Photobiology, American
Scientific Publishers, California, 2003.
Photochemistry, 36, 2007, 133–204 197
2. V. Ramamurthy and K.S. Schanze (ed.), Molecular and Supramolecular Photo-

chemistry, vol.9 (Photochemistry of Organic Molecules in Isotropic and Anisotropic
Media), Marcel Dekker, New York, 2003.
3. W. Horspool and F. Lenci (Ed.), CRC Handbook of Organic Photochemistry and
Photobiology, 2nd edn., CRC Press, Boca, Raton, Florida, 2003.
4. P. Schmoldt, H. Rinderhagen and J. Mattay, in ref. 1, p. 185.
5. S. Fukuzumi and H. Imahori, in ref. 2, p. 227.
6. A. Amini and A. Harriman, J. Photochem. Photobiol. C, 2003, 4, 155.
7. T. Kodama, I, Tomohiro and A.Y. Masaki, Gifu Yakka Daigaku Kiyo, 2003, 52, 1;
Chem Abstr., 2004, 140, 270341g.
8. M. Fagnoni, Heterocycles, 2003, 60, 1921.
9. E.L. Clennan, in ref. 2, p. 275.
10. S. Takada, H. Yamashita and M. Anpo, Hyomen, 2003, 41, 253; Chem Abstr.,
2004, 140, 67467k.
11. K.B. Yoon, in Handbook of Zeolite Science and Technology, ed. S.M. Auerbach,
K.A. Carrado and P.K. Dutta, Marcel Dekker, New York, 2003, p. 591.
12. J. Sivaguru, J. Shailaja and V. Ramamurthy, in ref. 11, p. 515.
13. M. Kojima, in ref. 1, p. 501.
14. V. Balzani, Photochem. Photobiol Sci., 2003, 2, 459.
15. E. van Faassen and D. Schlettwein, in ref. 1, p. 355.
16. S. Anandan and M. Yoon, J. Photochem. Photobiol. C., 2003, 4, 5.
17. K.S. Peters, in Advances in Photochemistry, vol. 27, D.C. Neckers, G. von Bunau
and W.S. Jenks, (ed.), John Wiley, New York, 2002, p.51.
18. S.A. Chesnokov, V.K. Cherkasov, G.A. Abakumov, Y.A. Kurskii, M.P. Shurygina,
O.N. Mamysheva and A.S. Shavyrin, Russ. Chem. Bull., 2003, 52, 718.
19. H. Goerner, Photochem. Photobiol., 2003, 78, 440.
20. O. Brahmia and C. Richard, Photochem. Photobiol. Sci., 2003, 2, 1038.
21. M. Kumbhakar, S. Nath, M.C. Rath, T. Mukherjee and H. Pal, Photochem.
Photobiol., 2004, 79, 1.
22. K. Kokubo and T. Oshima, in ref. 3, p. 74/1.
23. E. Hasegawa, N. Chiba, T. Takahashi, S. Takizawa, T. Kitayama and T. Suzuki,
Chem. Lett., 2004, 33, 18.
24. E. Hasegawa, J. Photosci., 2003, 10, 61.
25. P.B. Jones, J.L. Reynolds, R.G. Brinson and R.L. Butke, in ACS Symposium
Series, 856 (Ionic Liquids as Green Solvents), R.D. Rogers and K.R. Seddon, (ed.),
ACS, Washington, DC, 2003, p. 370.
26. J.-T. Li, J.-H. Yang, J.-F. Han and T.-S. Li, Green Chem., 2003, 5, 433.
27. D. Armesto, M.J. Ortiz, A.R. Agarrabeitia and M. Martin-Fontecha, Org. Lett.,
2004, 6, 2261.
28. K. Okamoto, Y. Araki, O. Ito and S. Fukuzumi, J. Am. Chem. Soc., 2004, 126, 56.
29. A. Albini and M. Fagnoni, in ref. 3, p. 99/1.
30. W. Adam and A.V. Trofimov, in ref. 3, p. 93/1.
31. V. Brezova, P. Tarabek, D. Dvoranova, A. Stasko and S. Biskupic, J. Photochem.
Photobiol., A, 2003, 155, 179.
32. E. Norambuena, C. Olea-Azar, A.M. Rufs and M.V. Encinas, Phys. Chem. Chem.
Phys., 2004, 6, 1230.
33. H. Gorner and D. Dopp, J. Photochem. Photobiol., A, 2003, 159, 219.
34. S.V. Zelentsov, N.V. Zelentsova, M.V. Kuznetsov and I.V. Simdyanov, High
Energy Chem., 2004, 38, 25.
198 Photochemistry, 36, 2007, 133–204
35. C. Chatgilialoglu, M. Duca, C. Ferreri, M. Guerra, M. Ioele, Q.G. Mulazzani,

H. Strittmatter and B. Giese, Chem.-Eur. J., 2004, 10, 1249.
36. M. Oelgemoeller and A.G. Griesbeck, in ref. 3, p. 84/1.
37. A.G. Griesbeck and S. Schieffer, Photochem. Photobiol Sci., 2003, 2, 113.
38. G. Jones and S. Kumar, J. Photochem. Photobiol., A, 2003, 160, 139.
39. P.G. Potvin, P.U. Luyen and J. Braeckow, J. Am. Chem. Soc., 2003, 125, 4894.
40. S. Sortino, S. Petralia and S. Di Bella, J. Am. Chem. Soc., 2003, 125, 5610.
41. C.-C. Cheng, W.-S. Yu, P.-T. Chou, S.-M. Peng, G.-H. Lee, P.-C. Wu, Y.-H. Song
and Y. Chi, Chem. Commun., 2003, 2628.
42. A.C. Benniston, M. Davies, A. Harriman and C. Sams, J. Phys. Chem. A., 2003,
107, 4669.
43. Y. Kubo, M. Kato, Y. Misawa and S. Tokita, Tetrahedron Lett., 2004, 45, 3769.
44. M. Boiocchi, G. Colucci, M. Licchelli, E. Monzani and D. Sacchi, Chem. Commun.,
2003, 2906.
45. K. Suzuki, H. Shiroishi, M. Hoshino and M. Kaneko, J. Phys. Chem. A, 2003, 107,
5523.
46. X. Li, H. Wang, K. Inoue, M. Uehara, H. Nakamura, M. Miyazaki, E. Abe and
H. Maeda, Chem. Commun., 2003, 964.
47. K. Kim, I. Lee and S.J. Lee, Chem. Phys. Lett., 2003, 377, 201.
48. R. Suau, R. Garcia-Segura, C. Sanchez-Sanchez, E. Perez-Inestrosa and
A.M. Pedraza, Tetrahedron, 2003, 59, 2913.
49. U.C. Yoon, Y.X. Jin, S.W. Oh, C.H. Park, J.H. Park, C.F. Campana, X. Cai,
E.N. Duesler and P.S. Mariano, J. Am. Chem. Soc., 2003, 125, 10664.
50. H. Liu, X. Zhang, C. Wang, W. Guo, Y. Wu and S. Yang, J. Phys. Chem. A, 2004,
108, 3356.
51. Q.H. Song, X. Hei, Z. Xu, X. Zhang and Q. Guo, Bioorg. Chem., 2003, 31, 357.
52. T. Tamai, T. Hayamizu and K. Mizuno, in ref. 1, p. 125.
53. T. Miura, Y. Urano, K. Tanaka, T. Nagano, K. Ohkubo and S. Fukuzumi, J. Am.
Chem. Soc., 2003, 125, 8666.
54. D.M. Guldi, M. Marcaccio, D. Paolucci, F. Paolucci, N. Tagmatarchis, D. Tasis,
E. Vazquez and M. Prato, Angew. Chem., Int. Ed., 2003, 42, 4206.
55. P. Vanalabhpatana and D.G. Peters, Tetrahedron Lett., 2003, 44, 3245.
56. Y. Sumino, N. Harato, Y. Tomisaka and A. Ogawa, Tetrahedron, 2003, 59,
10499.
57. A.S.K. Hashmi, L. Ding, J.W. Bats, P. Fischer and W. Frey, Chem.–Eur. J., 2003,
9, 4339.
58. S.E. Vaillard, A. Postigo and R.A. Rossi, J. Org. Chem., 2004, 69, 2037.
59. N. Tzvetkov, M. Schmidtmann, A. Muller and J. Mattay, Tetrahedron Lett., 2003,
44, 5979.
60. A.C. Beveridge, B.A. Bench, S.M. Gorun and G.J. Diebold, J. Phys. Chem. A,
2003, 107, 5138.
61. B.R. Renikuntla, H.C. Rose, J. Eldo, A.S. Waggoner and B.A. Armitage, Org.
Lett., 2004, 6, 909.
62. P.F. Santos, L.V. Reis, P. Almeida, A.S. Oliveira and L.F. Vieira Ferreira,
J. Photochem. Photobiol., A, 2003, 160, 159.
63. M. Korinek, R. Dedic, A. Svoboda and J. Hala, J. Fluorescence, 2004, 14, 71.
64. I. Roy, T.Y. Ohulchanskyy, H.E. Pudavar, E.J. Bergey, A.R. Oseroff, J. Morgan,
T.J. Dougherty and P.N. Prasad, J. Am. Chem. Soc., 2003, 125, 7860.
65. F. Mitzel, S. FitzGerald, A. Beeby and R. Faust, Chem.–Eur. J., 2003, 9, 1233.
66. F. Mitzel, S. FitzGerald, A. Beeby and R. Faust, Eur. J. Org. Chem., 2004, 1136.
Photochemistry, 36, 2007, 133–204 199
67. Y. You, S.L. Gibson, R. Hilf, S.R. Davies, A.R. Oseroff, I. Roy, T.Y. Ohulchanskyy,
E.J. Bergey and M.R. Detty, J. Med. Chem., 2003, 46, 3734.
68. Y. Mikata, S. Takagi, M. Tanahashi, S. Ishii, M. Obata, Y. Miyamoto, K. Wakita,
T. Nishisaka, T. Hirano, T. Ito, M. Hoshino, C. Ohtsuki, M. Tanihara and S. Yano,
Bioorg. Med. Chem. Lett., 2003, 13, 3289.
69. J.-H. Zhou, S.-Q. Xia, J.-R. Chen, X.-S. Wang and B.-W. Zhang, Chem. Commun.,
2003, 1372.
70. A.K. Patra, S. Dhar, M. Nethaji and A.R. Chakravarty, Chem. Commun., 2003, 1562.
71. M.S. Galletero, H. Garcia and J.L. Bourdelande, Chem. Phys. Lett., 2003, 370, 829.
72. A.A. Abdel-Shafi, D.R. Worrall and A.Y. Ershov, Dalton Trans., 2004, 30.
73. T. Tsubomura, M. Abe, M. Tarutani, H. Yamada and T. Tsukuda, Bull. Chem.
Soc. Jpn., 2003, 76, 2151.
74. C.G. Martinez, A. Neuner, C. Marti, S. Nonell, A.M. Braun and E. Oliveros, Helv.
Chim. Acta., 2003, 86, 384.
75. Y. Nosaka, T. Daimon, A.Y. Nosaka and Y. Murakami, Phys. Chem. Chem.
Phys., 2004, 6, 2917.
76. W. Adam, S. Bosio, A. Bartoschek and A.G. Griesbeck, in ref. 3, p. 25/1.
77. A.G. Griesbeck, W. Adam, A. Bartoschek and T.T. El-Idreesy, Photochem.
Photobiol Sci., 2003, 2, 877.
78. S. Jockusch, R.X. Ren, Y.P. Jang, Y. Itagaki, H.R. Vollmer-Snarr, J.R. Sparrow,
K. Nakanishi and N.J. Turro, J. Am. Chem. Soc., 2003, 125, 4646.
79. V.H. Grassian and S.C. Larsen, in ref. 1, vol. 3, p. 451.
80. V. Ramamurthy, J. Shailaja, L.S. Kaanumalle, R.B. Sunoj and J. Chandrasekhar,
Chem. Commun., 2003, 1987.
81. J. Vakros, G. Panagiotou, C. Kordulis, A. Lycourghiotis, G.C. Vougioukalakis,
Y. Angelis and M. Orfanopoulos, Catal. Lett., 2003, 89, 269.
82. D. Zhang, L.-Z. Wu, Q.-Z. Yang, X.-H. Li, L.-P. Zhang and C.-H. Tung, Org.
Lett., 2003, 5, 3221.
83. Y. Kara and M. Balci, Tetrahedron, 2003, 59, 2063.
84. M.S. Gultekin, E. Salamci and M. Balci, Carbohydr. Res., 2003, 338, 1615.
85. I. Nagy, D. Konya, Z. Riedl, A. Kotschy, G. Timari, A. Messmer and G. Hajos,
Tetrahedron, 2003, 59, 7485.
86. O. Sharon and A.A. Frimer, Tetrahedron, 2003, 59, 8153.
87. T. Suzuki, M.D. Friesen and H. Ohshima, Bioorg. Med. Chem., 2003, 11, 2157.
88. Y. Li, H.-Y. Hu, J.-P. Ye, H.-K. Fun, H.-W. Hu and J.-H. Xu, J. Org. Chem.,
2004, 69, 2332.
89. S.M. Bonesi, M. Fagnoni and A. Albini, J. Org. Chem., 2004, 69, 928.
90. F. Aydogan and A.S. Demir, Tetrahedron: Asymmetry, 2004, 15, 259.
91. P.S. Baran, C.A. Guerrero and E.J. Corey, J. Am. Chem. Soc., 2003, 125, 5628.
92. R. Schobert, R. Stehle and W. Milius, J. Org. Chem., 2003, 68, 9827.
93. J.-J. Helesbeux, O. Duval, C. Dartiguelongue, D. Seraphin, J.-M. Oger and
P. Richomme, Tetrahedron, 2004, 60, 2293.
94. D. Jiang, H. Zhao, S. Zhang and R. John, J. Phys. Chem. B, 2003, 107, 12774.
95. J. Yu, J. Chen, C. Li, X. Wang, B. Zhang and H. Ding, J. Phys. Chem. B, 2004,
108, 2781.
96. J.L. Gole, J.D. Stout, C. Burda, Y. Lou and X. Chen, J. Phys. Chem. B, 2004
108, 1274.
97. H. Haick and Y. Paz, ChemPhysChem, 2003, 4, 617.
98. K. Teramura, T. Tanaka, M. Kani, T. Hosokawa and T. Funabiki, J. Mol. Catal.
A Chem., 2004, 208, 299.
200 Photochemistry, 36, 2007, 133–204
99. L. Cermenati, D. Dondi, M. Fagnoni and A. Albini, Tetrahedron, 2003, 59, 6409.
100. S. Kim, H. Park and W. Choi, J. Phys. Chem. B., 2004, 108, 6402.
101. C. Tanielian, C. Schweitzer, R. Seghrouchni, M. Esch and R. Mechin, Photochem.
Photobiol. Sci., 2003, 297.
102. I.N. Lykakis, C. Tanielian and and M. Orfanopoulos, Org. Lett., 2003, 5, 2875.
103. I.N. Lykakis, S. Lestakis and M. Orfanopoulos, Tetrahedron Lett., 2003, 44, 6247.
104. D. Dondi, M. Fagnoni, A. Molinari, A. Maldotti and A. Albini, Chem.–Eur.
J., 2004, 10, 142.
105. A. Maldotti, R. Amadelli, I. Vitali, L. Borgatti and A. Molinari, J. Mol. Catal. A:
Chem., 2003, 204–205, 703.
106. H. Hori, E. Hayakawa, K. Koike, H. Einaga and T. Ibusuki, J. Mol. Catal. A:
Chem., 2004, 211, 35.
107. J. Saltiel, G. Krishnamoorthy, Z. Huang, D.-H. Ko and S. Wang, Can. J. Chem.,
2003, 81, 673.
108. D. Dondi, I. Caprioli, M. Fagnoni, M. Mella and A. Albini, Tetrahedron, 2003
59, 947.
109. M.S. Bjelakovic, L.B. Lorenc, V.D. Pavlovic, B. Tinant, J.-P. Declercq and
J. Kalvoda, Helv. Chim. Acta., 2003, 86, 2121.
110. B. Levrand and A. Herrmann, Photochem. Photobiol. Sci., 2002, 1, 907.
111. S.-I. Naya, H. Miyama, K. Yasu, T. Takayasu and M. Nitta, Tetrahedron, 2003,
59, 1811.
112. S.-I. Naya, H. Miyama, K. Yasu, T. Takayasu and M. Nitta, Tetrahedron, 2003,
59, 4929.
113. M.A. Miranda and M. Angeles Izquierdo, Photochem. Photobiol. Sci., 2003
848.
114. H. Ikeda, K. Akiyama, Y. Takahashi, T. Nakamura, S. Ishizaki, Y. Shiratori,
H. Ohaku, J.L. Goodman, A. Houmam, D.D.M. Wayner, S. Tero-Kubota and
T. Miyashi, J. Am. Chem. Soc., 2003, 125, 9147.
115. H. Ikeda, F. Tanaka, K. Akiyama, S. Tero-Kubota and T. Miyashi, J. Am. Chem.
Soc., 2004, 126, 414.
116. K. Mizuno, K. Nakanishi, Y. Otsuji, T. Hayamizu, H. Maeda, T. Adachi, A. Ishida
and A. S. Takamuku, J. Photosci., 2003, 10, 121.
117. H. Maeda, S. Nishioka and K. Mizuno, Tetrahedron Lett., 2003, 44, 6601.
118. S.N. Smirnov, P.A. Liddell, I. V. Vlassiouk, A. Teslja, D. Kuciauskas, C.L. Braun,
A.L. Moore, T.A. Moore and D. Gust, J. Phys. Chem. A, 2003, 107, 7567.
119. Z. Pengyi, L. Fuyan, Y. Gang, C. Qing and Z. Wanpeng, J. Photochem. Photobiol.
A, 2003, 156, 189.
120. T. Ohno, M. Akiyoshi, T. Umebayashi, K. Asai, T. Mitsui and M. Matsumura,
Appl. Catal. A, 2004, 265, 115.
121. Y. Xu and Z. Chen, Chem. Lett., 2003, 33, 592.
122. Y. Huang, W. Ma, J. Li, M. Cheng, J. Zhao, L. Wan and J.C. Yu, J. Phys. Chem.
B, 2003, 107, 9409.
123. G. Lente and J.H. Espenson, Chem. Commun., 2003, 1162.
124. T. Ruether, V.M. Hultgren, B.P. Timko, A.M. Bond, W.R. Jackson and
A.G. Wedd, J. Am. Chem. Soc., 2003, 125, 10133.
125. T. Ruether, A.M. Bond and W.R. Jackson, Green Chem., 2003, 5, 364.
126. H. Park and W. Choi, J. Phys. Chem. B, 2004, 108, 4086.
127. H. Tada, A. Kokubu, M. Iwasaki and S. Ito, Langmuir, 2004, 20, 4665.
128. T. Tachikawa, S. Tojo, M. Fujitsuka and T. Majima, Tetrahedron Lett., 2004
45, 3753.
Photochemistry, 36, 2007, 133–204 201
129. G. Ramakrishna, A.K. Singh, D.K. Palit and H.N. Ghosh, J. Phys. Chem. B, 2004,
108, 1701.
130. H, Maeda, H. Miyamoto and K. Mizuno, Chem. Lett., 2004, 33, 462.
131. H. Maeda, H. Nakagawa and K. Mizuno, Photochem. Photobiol. Sci., 2003, 2, 1056.
132. E.L. Clennan and G. Pan, Org. Lett., 2003, 5, 4979.
133. J. Li, W. Ma, Y. Huang, M. Cheng, J. Zhao and J.C. Yu, Chem. Commun.,
2003, 2214.
134. A. Itoh, T. Kodama, S. Hashimoto and Y. Masaki, Synthesis, 2003, 15, 2289.
135. K. Ohkubo, K. Suga, K. Morikawa and S. Fukuzumi, J. Am. Chem. Soc., 2003,
125, 12850.
136. K. Suga, K. Ohkubo and S. Fukuzumi, J. Phys. Chem. A, 2003, 107, 4339.
137. S. Fukuzumi, J. Yuasa, N. Satoh and T. Suenobu, J. Am. Chem. Soc., 2004
126, 7585.
138. J. von Sonntag, E. Mvula, K. Hildenbrand and C. von Sonntag, Chem.-Eur. J.,
2004, 10, 440.
139. P. Montana, N. Pappano, N. Debattista, V. Avila, A. Posadaz, S.G. Bertolotti and
N.A. Garcia, Can. J. Chem., 2003, 81, 909.
140. A.L. Macanita, F. Elisei, G.G. Aloisi, F. Ortica, V. Bonifacio, A. Dias, E. Leitao,
M.J. Caldeira, C.D. Maycock and R.S. Becker, Photochem. Photobiol., 2003, 77, 22.
141. F.M. Cabrerizo, A.H. Thomas, C. Lorente, M.L. Dantola, G. Petroselti,
R. Erra-Balsells and A.L. Capparelli, Helv. Chim. Acta, 2004, 87, 349.
142. M. Mazur and G.J. Blanchard, J. Phys. Chem. B, 2004, 108, 1038.
143. M. Yasuda, R. Kojima, H. Tsutsui, D. Utsunomiya, K. Ishii, K. Jinnouchi,
T. Shiragami and T. Yamashita, J. Org. Chem., 2003, 68, 7618.
144. H. Ikeda, Y. Hoshi, Y. Kikuchi, F. Tanaka and T. Miyashi, Org. Lett., 2004, 6, 1029.
145. S. Kiau, G. Liu, D. Shukla, J.P. Dinnocenzo, R.H. Young and S. Farid, J. Phys.
Chem. A, 2003, 107, 3625.
146. H. Saito, T. Mori, T. Wada and Y. Inoue, J. Am. Chem. Soc., 2004, 126, 1900.
147. S. Fukuzumi, T. Okamoto and K. Ohkubo, J. Phys. Chem. A, 2003, 107, 5412.
148. V. Rosales, J. Zambrano and M. Demuth, Eur. J. Org. Chem., 2004, 1798.
149. B. Jing and D. Zhu, Tetrahedron Lett., 2004, 45, 221.
150. A.C. Benniston, A. Harriman, D.J. Lawrie and A. Mayeux, Phys. Chem. Chem.
Phys., 2004, 6, 51.
151. B.K. Kaletas, R. Dobrawa, A. Sautter, F. Wuerthner, M. Zimine, L. De Cola and
R.M. Williams, J. Phys. Chem. A, 2004, 108, 1900.
152. T.J. Chow, N.-R. Chiu, H.-C. Chen, C.-Y. Chen, W.-S. Yu, Y.-M. Cheng,
C.-C. Cheng, C.-P. Chang and P.-T. Chou, Tetrahedron, 2003, 59, 5719.
153. S. Fukuzumi, H. Kotani, K. Ohkubo, S. Ogo, N.V. Tkachenko and H. Lemmetyinen,
J. Am. Chem. Soc., 2003, 125, 1600.
154. B. Jing, M. Zhang and T. Shen, Org. Lett., 2003, 5, 3709.
155. D. Collado, E. Perez-Inestrosa and R. Suau, J. Org. Chem., 2003, 68, 3574.
156. G.M. Reddy, S.-Y. Chen and B.-J. Uang, Synthesis, 2003, 15, 497.
157. C. Sanchez-Martinez, M.M. Faul, C. Shih, K.A. Sullivan, J. L. Grutsch,
J.T. Cooper and S.P. Kolis, J. Org. Chem., 2003, 68, 8008.
158. O.A. Fedorova, Y.V. Fedorov, E.N. Andryukhina, S.P. Gromov, M.V. Alfimov
and R. Lapouyade, Org. Lett., 2003, 5, 4533.
159. N. Ocal, L.M. Yano and I. Erden, Tetrahedron Lett., 2003, 44, 6947.
160. S.-I. Naya, Y. Iida and M. Nitta, Tetrahedron, 2004, 60, 459.
161. Y. Mitsumoto and M. Nitta, J. Org. Chem., 2004, 69, 1256.
162. C.P. Butts and M. Jazdzyk, Chem. Commun., 2003, 1530.
202 Photochemistry, 36, 2007, 133–204
163. S. Fukuzumi, Pure Appl. Chem., 2003, 75, 577.

164. U.C. Yoon, Z. Su and P.S. Mariano, in ref. 3, p. 101/1.
165. D. Armesto, M.J. Ortiz and A.R. Agarrabeitia, in ref. 3, p. 95/1.
166. D. Armesto, O. Caballero, M. J. Ortiz, A.R. Agarrabeitia, M. Martin-Fontecha
and M.R. Torres, J. Org. Chem., 2003, 68, 6661.
167. B.A. Sparano, S.P. Shahi and K. Koide, Org. Lett., 2004, 6, 1947.
168. M.C.D. Manickam, K. Pitchumani and C. Srinivasan, Proc. Indian Acad. Sci.
Chem. Sci., 2003, 115, 273.
169. K. Maekawa, K. Kubo, T. Igarashi and T. Sakurai, Tetrahedron, 2004, 60, 1183.
170. N. Basaric, Z. Marinic and M. Sindler-Kulyk, Tetrahedron Lett., 2003, 44, 7337.
171. N. Basaric, Z. Marinic, A. Visnjevac, B. Kojic-Prodic, A.G. Griesbeck and
M. Sindler-Kulyk, Photochem. Photobiol. Sci., 2002, 1, 1017.
172. N. Armaroli, Developments in Fullerene Science, 2002, 4 (Fullerenes: From
Synthesis to Optoelectronic Properties), 137.
173. H. Imahori, Y. Mori and Y. Matano, J. Photochem. Photobiol., C, 2003, 4, 51.
174. Y. Kashiwagi, K. Ohkubo, J.A. McDonald, I.M. Blake, M.J. Crossley, Y. Araki,
O. Ito, H. Imahori and S. Fukuzumi, Org. Lett., 2003, 5, 2719.
175. K. Ohkubo, H. Kotani, J. Shao, Z. Ou, K.M. Kadish, G. Li, R.K. Pandey,
M. Fujitsuka, O. Ito, H. Imahori and S. Fukuzumi, Angew. Chem., Int. Ed., 2004
43, 853.
176. D. Bonifazi, M. Scholl, F. Song, L. Echegoyen, G. Accorsi, N. Armaroli and
F. Diederich, Angew. Chem., Int. Ed., 2003, 42, 4966.
177. N.P. Redmore, I.V. Rubtsov and M.J. Therien, J. Am. Chem. Soc., 2003125, 8769.
178. N. Yoshida, T. Ishizuka, K. Yofu, M. Murakami, H. Miyasaka, T. Okada,
Y. Nagata, A. Itaya, H.S. Cho, D. Kim and A. Osuka, Chem.-Eur. J., 2003, 9, 2854.
179. K. Okamoto, Y. Mori, H. Yamada, H. Imahori and S. Fukuzumi, Chem.-Eur. J.,
2004, 10, 474.
180. Y. Terazono, G. Kodis, J. Andreasson, G. Jeong, A. Brune, T. Hartmann, H. Duerr,
A.L. Moore, T.A. Moore and D. Gust, J. Phys. Chem. B, 2004, 108, 1812.
181. S. Fukuzumi, K. Ohkubo, W.E.Z. Ou, J. Shao, K.M. Kadish, J.A. Hutchison,
K.P. Ghiggino, P.J. Sintic and M.J. Crossley, J. Am. Chem. Soc., 2003, 125, 14984.
182. T. Makinoshima, M. Fujitsuka, M. Sasaki, Y. Araki, O. Ito, S. Ito and N. Morita,
J. Phys. Chem. B, 2004, 108, 368.
183. W.D. Oosterbaan, P.C.M. van Gerven, C.A. van Walree, M. Koeberg, J.J. Piet,
R.W.A. Havenith, J.W. Zwikker, L.W. Jenneskens and R. Gleiter, Eur. J. Org.
Chem., 2003, 3117.
184. L.-P. Zhang, B. Chen, L.-Z. Wu, C.-H. Tung, H. Cao and Y. Tanimoto, Chem.-Eur.
J., 2003, 9, 2763.
185. U.C. Yoon, H.C. Kwon, T.G. Hyung, K.H. Choi, S.W. Oh, S. Yang, Z. Zhao and
P.S. Mariano, J. Am. Chem. Soc., 2004, 126, 1110.
186. P. Piotrowiak, E. Galoppini, Q. Wei, G.J. Meyer and P. Wiewior, J. Am. Chem.
Soc., 2003, 125, 5278.
187. R. Gronheid, A. Stefan, M. Cotlet, J. Hofkens, J. Qu, K. Muellen, M. Van der
Auweraer, J.W. Verhoeven and F.C. De Schryver, Angew. Chem., Int. Ed., 2003,
42, 4209.
188. M.-S. Choi, T. Aida, H. Luo, Y. Araki and O. Ito, Angew. Chem., Int. Ed., 2003,
42, 4060.
189. M. Andersson, L.E. Sinks, R.T. Hayes, Y. Zhao and M.R. Wasielewski, Angew.
Chem., Int. Ed., 2003, 42, 3139.
Photochemistry, 36, 2007, 133–204 203
190. Y.-H. Wang, M.-Z. Zhu, X.-Y. Ding, J.-P. Ye, L. Liu and Q.-X. Guo, J. Phys.
Chem. B, 2003, 107, 14087.
191. K. Li, D.I. Schuster, D.M. Guldi, M.A. Herranz and L. Echegoyen, J. Am. Chem.
Soc., 2004, 126, 3388.
192. N. Watanabe, N. Kihara, Y. Furusho, T. Takata, Y. Araki and O. Ito, Angew.
Chem., Int. Ed., 2003, 42, 681.
193. P.N. Taylor, A.J. Hagan and H.L. Anderson, Org. Biomol. Chem., 2003, 1, 3851.
194. M. Alvaro, B. Ferrer, H. Garcia, E.J. Palomares, V. Balzani, A. Credi, M. Venturi,
J.F. Stoddart and S. Wenger, J. Phys. Chem. B, 2003, 107, 14319.
195. M. Sauer, Angew. Chem. Int. Ed., 2003, 42, 1790.
196. S. Arimori, M.D. Phillips and T.D. James, Tetrahedron Lett., 2004, 45, 1539.
197. A.J. Pearson and W. Xiao, J. Org. Chem., 2003, 68, 5361.
198. A.J. Pearson and W. Xiao, J. Org. Chem., 2003, 68, 5369.
199. T. Gunnlaugsson, T.C. Lee and R. Parkesh, Org. Biomol. Chem., 2003, 1, 3265.
200. T. Gunnlaugsson, P.E. Kruger, T.C. Lee, R. Parkesh, F.M. Pfeffer and
G.M. Hussey, Tetrahedron Lett., 2003, 44, 6575.
201. T. Kalai, E. Hideg, J. Jeko and K. Hideg, Tetrahedron Lett., 2003, 44, 8497.
202. A. Coskun, B.T. Baytekin and E.U. Akkaya, Tetrahedron Lett., 2003, 44, 5649.
203. S.K. Kim, N.J. Singh, S.J. Kim, H.G. Kim, J.K. Kim, J.W. Lee, K.S. Kim and
J. Yoon, Org. Lett., 2003, 5, 2083.
204. M. Sun, Ming, D.H. Shang Guan, H.M. Ma, L.H. Nie, X.H. Li and S.X. Xiong,
Chin. Chem Lett., 2003, 14, 1024.
205. U.C. Yoon and P.S. Mariano, in ref. 3, p. 85/1.
206. J.O. Bunte and J. Mattay, in ref. 3, p. 10/1.
207. J.O. Bunte, S. Rinne and J. Mattay, Synthesis, 2004, 619.
208. H. Rinderhagen and J. Mattay, Chem.-Eur. J., 2004, 10, 851.
209. M. Ganesan, V.K. Sivasubramanian, S. Rajagopal and R. Ramaraj, Tetrahedron,
2004, 60, 1921.
210. E. Baciocchi, T. Del Giacco, F. Elisei, M.F. Gerini, M. Guerra, A. Lapi and
P. Liberali, J. Am. Chem. Soc., 2003, 125, 16444.
211. N. Sofikiti, C. Rabalakos and M. Stratakis, Tetrahedron Lett., 2004, 45, 1335.
212. N. Sofikiti and M. Stratakis, ARKIVOC, 2003(iv), 30; (URL: http://www.
arkat-usa.org/ark/journal/2003/I06_Varvoglis/AV-672A/672A.asp).
213. A. Wrzyszczynski, M. Pietrzak, J. Bartoszewicz, H. Kozubek, G.L. Hug,
B. Marciniak and J. Paczkowski, J. Am. Chem. Soc., 2003, 125, 11182.
214. J.-M. Zen, S.-L. Liou, A.S. Kumar and M.-S. Hsia, Angew. Chem. Int. Ed., 2003,
42, 577.
215. M.H. Habibi, S. Tangestaninejad, I. Mohammadpoor-Baltork and M. Mont-
azerozohori, Phosphorus, Sulfur Silicon Relat. Elem., 2004, 179, 597.
216. M. Segura, L. Sanchez, J. De Mendoza, N. Martin and D.M. Guldi, J. Am. Chem.
Soc., 2003, 125, 15093.
217. D. Kreher, P. Hudhomme, A. Gorgues, H. Luo, Y. Araki and O. Ito, Phys. Chem.
Chem. Phys., 2003, 5, 4583.
218. G.A. Burley, A.G. Avent, O.V. Boltalina, I.V. Gol’dt, D.M. Guldi, M. Marcaccio,
F. Paolucci, D. Paolucci and R. Taylor, Chem. Commun., 2003, 148.
219. K. Yamanaka, M. Fujitsuka, Y. Araki, O. Ito, T. Aoshima, T. Fukushima and
T. Miyashi, J. Phys. Chem. A, 2004, 108, 250.
220. X. Guo, Z. Gan, H. Luo, Y. Araki, D. Zhang, D. Zhu and O. Ito, J. Phys. Chem.
A, 2003, 107, 9747.
204 Photochemistry, 36, 2007, 133–204
221. X. Guo, D. Zhang, H. Zhang, Q. Fan, W. Xu, X. Ai, L. Fan and D. Zhu,
Tetrahedron, 2003, 59, 4843.
222. G. Zhang, D. Zhang, X. Guo and D. Zhu, Org. Lett., 2004, 6, 1209.
223. X. Guo, D. Zhang and D. Zhu, J. Phys. Chem. B, 2004, 108, 212.
224. P.L. Callaghan, R. Fernandez-Pacheco, N. Jasim, S. Lachaize, T.B. Marder,
R.N. Perutz, E. Rivalta and S. Sabo-Etienne, Chem. Commun., 2004, 242.
Photoelimination
BY IAN R. DUNKIN
Department of Pure and Applied Chemistry, University of Strathclyde, Thomas
Graham Building, 295 Cathedral Street, G1 1XL, Glasgow, UK
1 Introduction
This chapter deals with photoinduced fragmentations of organic and selected

organometallic compounds, and especially reactions accompanied by loss of
small molecules such as nitrogen, carbon monoxide or carbon dioxide.
Photodecompositions which produce two or more larger fragments and other
miscellaneous photoeliminations are reviewed in the final section. Photofrag-
mentations of carbonyl compounds taking place, for example, by Norrish Type
I and II processes, are discussed systematically in Chapter 1, although some
eliminations from carbonyl compounds are also included here, e.g. certain
decarbonylations and decarboxylations.
A major publication event in the field of photochemistry during the review
period was the appearance of the second, and much enlarged, edition of the
CRC Handbook of Organic Photochemistry and Photobiology.1 This compre-
hensive work comprises reviews of many topics, including several chapters on
various specific types of photoelimination, references to which are made in the
appropriate sections below. Of more general relevance to this chapter are
reviews of the matrix-isolation technique in photochemical studies,2 the matrix
photochemistry of small ring compounds,3 both of which include examples of
photoeliminations, and a chapter on photoremovable protecting groups.4
Two short historical reviews of the development of flash photolysis in George
Porter’s laboratory at Cambridge have been published, one dealing with applica-
tions to gas-phase systems,5 the other studies of triplet states and free radicals in
solution.6 A comparison of theories of reversible dissociation of molecules
following photoexcitation has been made on the basis of integral kinetic equa-
tions.7 A number of different theories were brought to the same integral form.
2 Elimination of Nitrogen from Azo Compounds and Analogues
For quite a number of years now, the study of photo-induced nitrogen

elimination from azoalkanes and analogues has appeared to be the exclusive
205
206 Photochemistry, 36, 2007, 205–231
domain of Waldemar Adam’s Würzburg group, who have published a long

series of detailed studies, especially on the mechanism of N2 elimination from
2,3-diazabicyclo[2.2.1]hept-2-enes. This and related work has been reviewed in
the CRC Handbook.8
In addition, an extensive theoretical study of the denitrogenation of di-
azabicycloheptene (1) (Scheme 1) has recently been reported.9 This made use of
CASPT2//CASSCF computations to investigate reaction pathways, and has
indicated that the exo-axial conformer of the intermediate diazenyl diradical (2)
is the primary photoproduct. Furthermore, it appears that (2) is located in a
shallow region of the ground-state potential energy surface, which provides
access to five different reaction pathways, and that production of the experi-
mentally observed inverted housane (3inv) is inconsistent with thermal
equilibration of (2), but rather requires an impulsive population of an axial-
to-equatorial pathway. Similarly, the decrease of inversion stereoselectivity or
even the retention (the so-called stereochemical memory effect) observed for
certain substituted derivatives of (1) can be explained by dynamic effects, in
which the axial-to-equatorial motion is restrained by either inertia or steric
hindrance of the substituents. On the back of a large body of previously
published experimental results, this theoretical study must be regarded as
providing significantly enhanced understanding. Hitherto it was not well
understood how a photoreaction of this type, i.e., an elimination in which a
large amount of energy is deposited by the initial photon absorption, could
show such high degrees of stereoselectivity.
(3ret)
−N2 retention
(stereochemical memory)
N hν N N −N2
N inversion
(1) (2) (3inv)
stereochemical
−N2
memory loss
(3ret) (3inv)
Scheme 1
Further experimental corroboration of the intermediacy of diazenyl dirad-

icals, such as (2), has been provided by an investigation of the viscosity
Photochemistry, 36, 2007, 205–231 207
dependence of both stereoselectivity and product selectivity in the photo-

elimination of N2 from a 7-spirocyclopropane-substituted derivative of (1).10
3 Elimination of Nitrogen from Diazo Compounds and Diazirines

3.1 Generation of Alkyl and Aryl Carbenes. – A review of recent experimental
and theoretical progress in the photochemistry of diazirines has been pub-
lished.11 These compounds, unlike their valence isomers, diazo compounds, are
relatively stable to most organic reagents and are reasonably stable in dilute
solutions, and are therefore useful photochemical and thermal precursors to
carbenes.
A number of diaryloxydiazirines (4: X ¼ Y ¼ H, MeO, Me, Cl; X ¼ H, Y ¼
MeO, Cl; X ¼ MeO, Y ¼ Cl) (Scheme 2) have been synthesized and their
thermolyses and photolyses investigated in various media.12 Although the
thermolysis of (4) afforded products only from the expected carbenes (6),
photolysis gave both carbenes (6) and aryloxy radicals by a-scission. The
fragmentation of diaryloxycarbenes (6) to aryloxy radicals appears to be
unprecedented and, moreover, thermodynamically improbable, as indicated
by computations. The authors suggest, therefore, that the a-scission takes place
from the excited state of the diazirine, which they depict as the ring-opened
diradical (5).
X O Ar1O Ar1O
N hν N −N2
N N
Y O Ar 2O Ar2O
(4) (5) (6)
−N2
α-scission
Ar1O + Ar2OC
Scheme 2
The brominated diaryldiazomethane (7) was found to be stable enough to

survive Suzuki coupling, thus allowing the synthesis of mono-, bis- and
tris(diazo) compounds, e.g. (8).13 The photoproducts of these diazo compounds
were characterized by EPR and SQUID measurements, which indicated that
triplet, quintet and septet ground-state species were generated from the mono-,
bis- and tris(diazo) precursors, respectively. Temperature-dependent EPR and
UV-visible measurements and also laser flash photolysis studies showed that all
three species are stable up to 160 K, and have half-lives of a few seconds in
solution at room temperature.
208 Photochemistry, 36, 2007, 205–231
N2 N2
N2
Br
(7)
(8)
N2
N
Cl Cl N Cl
N
(11) N
hν
N N2 N N
N N N
Cl Cl Cl
(9) (10) (12)
N N N
hν −HCl Cl
N N
N (11) N
N N
Cl Cl
(15) (14) (13)
Scheme 3
In earlier studies of the thermolysis and photolysis of m-phenylene-bis(chloro-

diazirine) (9) in the presence of 2-vinylpyridine (11) (Scheme 3), it was found that
the reaction proceeded in a stepwise fashion, with generation of a monocarbene
Photochemistry, 36, 2007, 205–231 209
(10), followed by a number of steps, as shown in Scheme 3, leading to the

indolizine derivative (14), and then by similar reaction of the second diazirine to
the bis(indolizine) (15). In semi-preparative conditions, however, the reaction
was reported to stop at (14), after formation of the first indolizine moiety. This
has potential synthetic utility, since routes to unsymmetrical products could then
be developed, but raises the question of why the second diazirine ring is
seemingly inert photochemically. Several possible answers to this question were
suggested, including screening of the second diazirine by the intense absorption
of the first indolizine, or localization of the excitation energy from the second
photon in the indolizine system of (14). In a new study of the photolysis of (9)
and (11),14 making use of laser flash photolysis and both absorption and
fluorescence monitoring, coupled with computations, it has been established
that, although the S1 state of (14) has the excitation localized largely in the
indolizine system as previously suggested, there is a higher excited state of (14)
that can be readily thermally populated from S1, in which the excitation energy is
localized on the diazirine. Indeed, the quantum yield for decomposition of the
diazirine ring of (14) was estimated as B0.5, and the conclusion is that the
indolizine ring does not effectively inhibit this photodecomposition. It seems
instead that the best explanation for the reluctance of the second diazirine ring to
react in more concentrated solutions is the formation and precipitation of the
hydrochoride of (11), which gives rise to turbidity and thus light scattering.
The photolysis of 3-pyridyldiazomethane (16) (Scheme 4) in an argon matrix
at 7–10 K gives the corresponding carbene (17).15 Further photolysis of (17)
generates the nitrile ylide (19) as the major product, providing a new example of
this recently discovered type of ring opening. A minor amount of the ring
expanded didehydroazepine (20) was also formed.
CHN2 CH
hν
N N N
(16) (17) (18)
C
CH
N N
CH
(19) (20)
Scheme 4
Derivatives of C60 for photoaffinity labelling studies have been synthesized,

including the cis and trans diazirine compounds (21a).16 The photochemical
properties of these are currently being studied in various applications. An
210 Photochemistry, 36, 2007, 205–231
analogue of tautomycin containing an aryl diazirine moiety has also been

synthesized for use as a photoaffinity probe.17
R N
N
a: R = CF3
Me
b: R = N3
N
O
Me
(21)
3.2 Photolysis of a-Diazo Carbonyl and Related Compounds. – The photo-

chemical reactivity of a-diazo carbonyl compounds has been reviewed, espe-
cially with respect to recent experimental and theoretical contributions to
furthering the understanding of the reaction mechanisms.18
The question of oxygen migration and the involvement of oxirene interme-
diates in the Wolff rearrangement has been addressed in two papers by Haiss
and Zeller.19,20 In the first of these, crossover experiments between isotopomers
of 2-diazo-1-oxo-1-phenyethane (22) (18O, 13C and D substituted) have estab-
lished that the partial oxygen migration observed in the Wolff rearrangement
products following photoelimination of N2, see for example (24) in Scheme 5, is
not the result of an intermolecular process.19 This is consistent with a carbene-
carbene rearrangement via an intermediate oxirene (23). The second study was
concerned with the Wolff rearrangement of 3-diazo-1,1,1-trifluoro-2-oxo-pro-
pane (25b) (Scheme 6).20 The trifluoromethyl group had been considered as
having a low tendency to migrate to a carbene centre, and this served to explain
why photolysis of the diazoester (25a) results in hydrogen abstraction, to give
(26), rather than rearrangement. On this basis, the observed Wolff rearrange-
ment of (25b) was assumed to involve equilibration of the initially formed
oxocarbene (28b) with the isomeric (30b) via oxirene (29b), followed by the
H H Ph
Ph H
Ph hν Ph 13 13C
C H
13 13
C N2 −N2 C
O
O O O
1-[13C]-(22) (23)
Ph Ph
13 13
O C C C O
H H
1-[13C]-(24) 2-[13C]-(24)
Scheme 5
Photochemistry, 36, 2007, 205–231 211
O O OR2
F3C
F3C OEt O
(26) (27)
(25a) (25b)
O
hν, R2OH hν, R2OH
1
F3C * R
N2
(25) a: R1 = CO2Et
b: R1 = H
c: R1 = H, * = 13C
(25b,c)
hν
O O
O
H * F3C
F3C * * H
F3C H
(28) (29) (30)
H F3C
O *
C *
C O
CF3 H
H2O H2 O
HO O
* CF3
F3C
O * OH
(31c) (32c)
Scheme 6
favourable migration of an H atom in (30b). An investigation of the photolysis

of the 13C-labelled isotopomer (25c) in water-saturated ether, however, has
shown that rearrangement of the oxocarbene (28c) occurs to only a minor
extent: from the ratio of the yields of the isolated isotopomeric acids (31c) and
(32c), it was estimated that 93.5% of the rearranged product was produced by
trifluoromethyl migration. As a consequence, it is proposed that the difference in
photochemical behaviour between (25a) and (25b) is likely to be due to a larger
singlet-triplet splitting in the oxocarbene (28b), which allows the intramolecular
Wolff rearrangement to compete efficiently with singlet-triplet interconversion.
The photochemistry of diazo Meldrum’s acid (33) (Scheme 7) has been
investigated experimentally and theoretically.21 Irradiation of (33) in MeOH
with 254 nm light results in efficient loss of N2 and Wolff rearrangement,
affording the ester (36) via the intermediate ketene (35). There was no product
derived from trapping of a singlet carbene, suggesting that the Wolff
212 Photochemistry, 36, 2007, 205–231
254 nm
O O
O O O O
N 355 nm 254 nm
N2
N ∆ −N2
O O O C
O O O
(34) (33) (35)
MeOH MeOH
triplet sens. triplet sens. MeOH
O
O O
O
O
O CO2Me
O
(37) (36)
Scheme 7
rearrangement is concerted with nitrogen loss. Irradiation of (33) in MeOH at

355 nm led almost exclusively to the isomerized diazirine (34). This isomer-
ization and the loss of N2 leading to Wolff rearrangement clearly occur from
two different electronic excited states. The diazirine (34) reverts to the diazo
precursor (33) on mild heating, while UV-irradiation of (34) yields a mixture of
the Wolff rearrangement product and the diazo isomer (33). From the product-
evolution profiles, it seems that the Wolff rearrangement, at least initially,
occurs directly from (34) and not via the diazo compound (33). Finally, triplet
sensitization of both (33) and (34) gives Meldrum’s acid (37), presumably via an
intermediate triplet carbene.
A laser flash-photolysis study has been made of the bis(arylsulfonyl)diazo-
methanes (38: X ¼ H, Me).22 Analysis of the results indicated the involvement
of two transient species, and a partitioning of the reaction pathway between the
sulfonyl analogue of the Wolff rearrangement and what seems to be intramo-
lecular carbene oxidation by a sulfonyl group.
N2
X S S X
O2 O2
(38)
4 Elimination of Nitrogen from Azides and Related Compounds
The photochemistry of organic azides has been reviewed.23 In addition to the

photolysis of alkyl, vinyl, acyl, aryl and heteroaryl azides, this review also
Photochemistry, 36, 2007, 205–231 213
covers the chemistry of singlet and triplet nitrenes and the photogeneration of
nitrenium ions.
Photolysis of 2-, 3- and 4-fluorophenylazide (39a,b,c) in aniline gives the
products (40), (41) and (42) in the yields shown in Scheme 8.24 With 2,6-
difluoro- and 2,3,4,5,6-pentafluorophenyl azide, however, ring expansion to
azepine products analogous to (42) is suppressed, and the corresponding
unsymmetrical azobenzenes (cf. 41) are formed in 50% and 55% yield, respec-
tively. The azobenzenes are presumed to arise from insertion of a singlet nitrene
into an N–H bond of aniline, followed by oxidation of the resulting hydrazine.
NH2
N NHPh
N3 NH N NPh
hν
+ +
PhN3
X X X X
(39) (40) (41) (42)
a: X = 2-F a: 8% a: 10% a: 15%
b: X = 3-F b: 12% b: – b: 15%
c: X = 4-F c: – c: – c: 30%
Scheme 8
When o-azidobenzoic acid and its potassium salt were photolysed in H2O,
EtOH, THF, EtOH-H2O or THF-H2O, the major product was 2,1-benzisoxazo-
lone, from intramolecular cyclization.25 Varying amounts of azepine products
were observed, depending on the solvent. Intramolecular nitrene cyclization was
also observed in the photolysis of the azido-functionalized cryptand (43), which
afforded the benzopyrazole (44) after an aerobic workup.26
The paper which reported the photo-induced ring opening of 3-pyridylcar-
bene (17) (see Section 3.1) also described a study of the matrix photolysis of 3-
azidopyridine (45) (Scheme 9).15 Irradiation of (45) at 222 nm in Ar at 7 K gave
a product with IR and UV absorptions which indicated that it was the ring-
opened ylide (47); two rotamers were identified. The ylide also underwent a 1,7-
H shift to give the ketenimine (48) in two rotameric forms.
N N3 N N N N
O
O
O O O O
(43) (44)
214 Photochemistry, 36, 2007, 205–231
N3 N
hν C C
N NH
N2
N N N N
CH C
(45) (46) (47) (48)
Scheme 9
A matrix-isolation investigation of the photolysis of azido- and di-

azidophenylethynes has been carried out.27 Simple ethynyl or phenylethenyl
substitution of phenyl azide has little effect on the reaction pathway, no matter
which regioisomer is considered. Thus irradiation (l 4 350 nm) of the meta-
ethynyl azides (49a) and (49b) in Ar matrices at 13 K affords the corresponding
triplet carbenes, which can be photochemically interconverted with the ‘normal’
ring-expanded dehydroazepine products (51a,b). Exactly analogous results were
obtained for the para isomers (50a) and (50b). On the other hand, with the
diazides (52), the regiochemistry of the azido substitution substantially affects
the products obtained. Whenever the two azido groups are placed in conjugating
positions with respect to each other – i.e., p,p 0 - (52a), p,o 0 - (52b) and o,o 0 - (52c) –
a quinoidal diimine diradical is obtained, e.g. (53) from (52b), or the stereo-
isomers (54) and (55) from (52c). The m,m 0 - and p,m 0 -isomers (52d,e), however,
both gave photoproducts with EPR spectra in good agreement with what was
expected for a dinitrene quintet state. In addition, (52d), but not (52e), gave a
dehydroazepine product, as indicated by the matrix IR spectrum.
CR
C
N
N3 N3 C CR C CR
(49) (50) (51)
a: R = H b: R = Ph
X Y
(52)
a: X = 4-N3; Y = 4′ -N3
b: X = 4-N3; Y = 2′ -N3
c: X = 2-N3; Y = 2 ′-N3
d: X = 3-N3; Y = 3′ -N3
e: X = 4-N3; Y = 3′ -N3
N N N N
N C C C C C C
N
(53) (54) (55)
Photochemistry, 36, 2007, 205–231 215
Quintet m-phenylenedinitrenes have been generated in low-temperature ma-

trices by photolysis of the corresponding diazide precursors, and their second-
ary photochemical transformations studied.28 Two competing ring-opening
pathways were identified, and it was also concluded that quintet dinitrenes are
much more photochemically reactive than triplet nitrenes. An EPR study of
radical intermediates formed in the photooxidation of 4,4 0 -diazidodiphenyl in
benzene and toluene has also been published.29 The radicals apparently arise by
abstraction of H atoms from the solvent by a triplet nitrene–O2 complexes.
Two related reports have been made on the generation of 2,4,6-trinitreno-
1,3,5-triazine, a septet trinitrene, by photolysis of the triazido precursor (56).30,31
Stepwise generation of the mono-, di- and trinitrene was observed in low-
temperature matrices by IR and EPR spectroscopy. Comparison of experimental
IR spectra with those calculated by DFT aided the assignments. The trinitrene
readily decomposed into three NCN molecules upon further irradiation.
N3
N N
N3 N N3
(56)
As well as the aziridine group in (21a) (see Section 3.1), an azide functionality
has also been incorporated into a C60 derivative (21b) for use as a photoaffinity
label.16
5 Photoelimination of Carbon Monoxide and Carbon Dioxide
A new statistical quantum mechanical approach – the statistical adiabatic

product distribution method – has been applied to the photodissociation of
ketene in parallel theoretical32 and experimental33 studies. The main focus of
the work, however, was H-atom production via C–H cleavage rather than the
elimination of CO. The photodecomposition of formohydroxamic acid
(HCONHOH) has been investigated in matrix-isolation FTIR and DFT stud-
ies.34 Irradiation of the acid in Ar or Xe matrices with the full output of a xenon
arc lamp generated H-bonded HNCO H2O and NH2OH CO complexes. In
the latter case, the IR spectra also suggest the existence of a structure with the
NH2 group interacting with the carbon atom.
The photochemistry of a-pyrone (57a) (Scheme 10) was the subject of some
of the earliest matrix-isolation studies of organic species. This system still has
some interest for further study, however, especially on account of the success
that DFT computations have had in assisting with the assignments of matrix IR
spectra. Recently, the matrix photolyses of both a-pyrone35 and its 4,6-di-
methyl derivative (57b)36 have been investigated with the aid of DFT calcula-
tions. When (57a) is irradiated (l 4 285 nm) in Ar or Kr matrices, rapid
formation of rotamers, (58a) and (59a), of the Z isomer of the ring-opened
216 Photochemistry, 36, 2007, 205–231
R R O
R O
hν O hν
R C O + O C O
hν O
O R R R
(58) (59) R
(57) (62)
hν
a: R = H hν
C O C O b: R = Me
R
+
O R R R + CO2
R O
R
(60) (61) (63)
Scheme 10
aldehyde-ketene results. Further irradiation generates rotamers of the E iso-

mer: (60a) and probably (61a). Upon subsequent irradiation at l 4 337 nm, the
Z forms revert to the ring-closed starting material (57a), but the E forms do not
react. At l 4 285 nm, the ring-opening reaction of (57a) is accompanied by a
much slower isomerization to the bicyclic lactone (62a), which in turn is
converted into cyclobutadiene (63a) and CO2 at shorter wavelengths (l 4
235 nm). These findings are in accord with those from previous investigations,
and the main novelty lies in the positive identification of particular isomers and
rotamers of the ring-opened product, which has now been made possible for the
first time. The matrix photochemistry of 4,6-dimethyl-a-pyrone (57b) is some-
thing of a contrast to that of the parent compound. Although both ring
opening and valence isomerization to the bicyclic lactone (62b) are observed
on UV irradiation (l 4 315 nm), the latter reaction is by far the more efficient.
1,3-Dimethylcyclobutadiene (63b) is generated from the lactone at shorter
wavelengths (l 4 235 nm).
The photochemistry of ketoprofen (64) has been studied because of the
known phototoxicity of this compound; the photoproduct is 3-ethylbenzophe-
none, formed via a short-lived carbanion (65). In a new study of this reaction,37
the lifetime of the carbanion has been extended to several hours by generating it
in carefully controlled conditions in THF. Intermolecular photoinduced dec-
arboxylative additions of alkylcarboxylates to N-substituted phthalimides gave
the corresponding hydroxyphthalimidines in yields of 39–89%.38 Time-
resolved monitoring on the fs-scale of transient intermediates in the photo-
decarboxylation of organic peroxides has been carried out in conjunction with
theoretical modelling.39,40
O Me O Me
CO2−
(64) (65)
Photochemistry, 36, 2007, 205–231 217
5.1 Photoelimination of CO from Organometallic Compounds. – A procedure

for the sunlight-induced synthesis of (Z2-C60)M(CO)5 complexes from fullerene
and M(CO)6 (M ¼ Mo, W) has been suggested as an instructive laboratory
experiment.41 Sequential loss of CO ligands has been observed in the formation
of W(CO)4(Z4-2,5-dimethylfuran) during laser photolysis (308 nm) of cyclo-
hexane solutions of W(CO)6 containing excess 2,5-dimethylfuran.42 An initially
generated unstable complex, W(CO)5(Z1-2,5-dimethylfuran) rapidly eliminated
a second CO molecule to give the final product in a first-order process. Near-
UV irradiation of Ru(dcbpy)I2(CO)2 in solution induces loss of one of the CO
groups, generating a vacant coordination site, which is occupied by a solvent
molecule.43 The kinetics of this ligand exchange in EtOH were studied with
femtosecond resolution, by probing the CO stretching vibrations of the reac-
tant and product molecules. It was found that photoelimination of CO occurs
on a sub-picosecond time scale, with an overall quantum yield well below unity
(0.3). Recovery of the parent molecule also occurs on a sub-picosecond time
scale.
Five new complexes, [M(CO)5(DTTT)] (M ¼ Cr, Mo, W), [Re
(CO)4Br(DTTT)] and [Mn(CO)2Cp(DTTT)], have been prepared by the pho-
tochemical reaction of the metal carbonyls M(CO)6 (M ¼ Cr, Mo, W),
Re(CO)5Br and Mn(CO)3Cp with 3,5-dimethyltetrahydro-2H-1,3,5-thiadia-
zine-2-thione (DTTT) (66).44 Spectroscopic and x-ray diffraction studies
showed that DTTT behaves as a monodentate ligand, coordinating to the
metal centre via the sulfur (C ¼ S) donor atom. Similar sulfur (P ¼ S) donation
has been observed in the novel complexes (68) and (69), obtained by photolysis
of Re(CO)5Br in the presence of tetraalkyldiphosphine disulfides (67: R ¼ Me,
Et, Pr, Bu, Ph) (Scheme 11).45 Analogous complexes have also been synthesized
in the photochemical reactions of Re(CO)5Br with diphosphines,
Ph2P(CH2)nPPh2 (n ¼ 1–3).46 Spectroscopic characterization of the products
suggests cis-chelate bidentate coordination of the ligand in fac-[Re
(CO)3Br{Ph2P(CH2)nPPh2}] (n ¼ 1–3), and cis-bridging bidentate coordination
between two metals in [Re2(CO)8Br2{cis-m-Ph2P(CH2)PPh2}] (n ¼ 1–3). Photo-
induced substitution of CO in iron selenocarboxylate complexes
CpFe(CO)2SeCOR with triphenylphosphine, -arsine or -antimony (EPh3) gave
exclusively and in high yields the monosubstituted products
CpFe(CO)(EPh3)SeCOR (R ¼ Ph, 2-Me-C6H4, 4-NO2-C6H4, 3,5-(NO2)2-
C6H3; E ¼ P, As, Sb).47
Me Me
N N
S S
(66)
5
Photochemical reaction of (m -C5Me5)Re(CO)3 with 2,4,5-trichloroanisole
and 3,4,5-trichlorotrifluoromethylbenzene yields (Z5-C5Me5)Re
5
(CO)2(C6H2Cl2(MeO))Cl and (Z -C5Me5)Re(CO)2(C6H2Cl2(CF3))Cl, respec-
tively, by insertion of the intermediate (Z5-C5Me5)Re(CO)2 into a C–Cl bond
218 Photochemistry, 36, 2007, 205–231
R R
Br S R Br S P S
R hν P
OC CO OC
Re + P P Re R R
OC CO R −CO OC CO
CO R S CO
(67)
−CO
R R
R R
R
Br S Br S Br
OC P R S
OC CO
Re Re Re
OC P R OC CO OC CO
CO S R CO CO
(68) (69)
Scheme 11
of the chloroarene.48 In the trichloroanisole, C–Cl bond activation occurs ortho

to the methoxy group, while the reaction with C6H2Cl3(CF3) occurs at the
chlorine meta to the CF3 group.
6 Photoelimination of NO and NO2
The past few years have seen a flurry of activity in research into the photo-
elimination of NOx species, particularly on account of the biological activity of
NO as well as interest in the environmental impact of nitrogen oxides. In the
period under review at present, however, only three reports concerning photo-
elimination of NO or NO2 have appeared.
A high-level theoretical study of low-lying singlet and triplet potential energy
surfaces in the photolysis of nitromethane has been carried out, which reinter-
prets available experimental results in a consistent manner.49 Two reaction
paths were found in the photolysis of CH3NO2 with 193 nm light, which
generates initially the 2A00 excited state. In the major channel, intersystem
crossing gives the 2A 0 state, which dissociates into CH3(1A 0 1) þ NO2(1 2B1); the
photoeliminated NO2 then undergoes intersystem crossing to the 1 2A1 state,
which dissociates into NO(A 2S1) and a mixture of O(3P) and O(1D). In the
minor channel, the initial 2A00 state of CH3NO2 dissociates directly into
CH3(1A 0 1) and NO2(1 2A2), which in turn gives NO(X 2P) and a mixture of
O(3P) and O(1D). No ionic species were implicated in any dissociation pathway.
The velocity and angular distributions of NO produced by UV photolysis of
nitrosobenzene have been determined by velocity-map ion imaging.50 With
light of l ¼ 290.5 (S2 state) and 226 nm (Sn (n Z 3) states), completely
isotropic velocity distributions were observed, leading to the conclusion that
photodissociation occurs on a timescale much slower than rotation of the
parent molecule, and after redistribution of the excess energy into the vibra-
tional modes.
Photochemistry, 36, 2007, 205–231 219
O O
N O hν N
Et2N N Et2N + NO
(70) (71)
H+ e− transfer
Et2NH + 2 NO Et2NNO + 3NO−
Scheme 12
The aqueous photochemistry of the sodium salt of 1-(N,N-diethylamino)dia-

zen-1-ium-1,2-diolate (70) (Scheme 12) has been examined experimentally and
theoretically.51 Photolysis of (70) results in formation of the radical anion (71)
and NO, via intersystem crossing and a triplet excited state. The product pair
either undergoes electron transfer, before escape of NO from the cage, to form
triplet NO and nitrosamine (minor pathway), or the radical anion (71)
dissociates to give a second NO molecule and (ultimately) diethylamine (major
pathway).
7 Miscellaneous Photoeliminations and Photofragmentations
7.1 Photoelimination from Hydrocarbons. – The visible fluorescence of excited

CH fragments in the A2D and B2S states has been observed following photo-
dissociation of ethene in the 11.7–1.4 eV energy range.52 Two channels were
identified: CH* þ CH3 and CH* þ H2, and it is proposed that both pass via an
ethylidene intermediate (H3CCH:). The photofragmentation dynamics of ethyne
have been studied via vibrationally mediated photodissociation.53 Near-IR
excitation prepared rovibrational states in the region of three C–H stretch
quanta (B9640 cm1 ), and subsequent irradiation at 243.1 nm dissociated these
pre-excited C2H2 molecules into C2HþH; the resulting H atoms were probed by
UV resonantly enhanced multiphoton ionization. An organic molecule contain-
ing krypton, HKrCCH, has been generated in low-temperature matrices by
193-nm irradiation of solidified mixtures of C2H2 and Kr at 8 K, and subsequent
thermal mobilization of the resulting H atoms by warming to Z 30 K.54 The
novel organokrypton species was characterized by IR absorption spectroscopy
and identified with the aid of ab initio calculations.
Photodissociation dynamics of propene at 157.6 nm have been investigated
in a molecular beam apparatus by photofragment translational spectroscopy.55
The eleven photofragments identified were assigned to eight dissociation
channels: C3H5 þ H, C3H4 þ H þ H, C3H4 þ H2, C3H3 þ H2 þ H, C2H4 þ
CH2, C2H3 þ CH3, C2H2 þ CH4 and C2H2 þ CH3 þ H, with branching ratios
of 1%, 7%, o0.2%, 17%, 6%, 4%, 5% and 60%, respectively. This somewhat
complicated process seemingly has a preference for triple dissociations, notably
to C2H2, CH3 and H. The photodissociation dynamics of CD3CH¼CH2 at the
same wavelength was also studied.56 Labelling of the methyl group with
220 Photochemistry, 36, 2007, 205–231
deuterium allowed discrimination between elimination of atomic and molecular

hydrogen from the vinyl and methyl moieties. Hydrogen migration before
photodissociation was also revealed by this means. The dynamics of allene and
propyne photofragmentation at 193.3 and 121.6 nm have been investigated by
H(D) Rydberg atom translational spectroscopy.48 The total kinetic energy-
release spectra for H2C¼C¼CH2, H3CCRCH and D3CCRCH photolysis at
193.3 nm were essentially identical – contradicting several previous studies of
propyne photochemistry at this wavelength. The results were most easily
rationalized by assuming that the fragmentations are preceded by internal
conversion to the S0 ground state, and that the isomerization rate of the
resulting highly vibrationally excited molecules exceeds that of the unimolec-
ular decay. The analogous spectra from 121.6 nm photolysis, however, are
significantly different. This observation can be accounted for by assuming two
competing pathways for propyne: one involving selective cleavage of the
H3CCC–H bond, the other arising via radiationless transfer to a lower excited
state, isomerization and then unimolecular decay.
The benzyl radical and several deuteriated isotopomers have been generated
in methylcyclohexane at 4.2 K by UV-photolysis of toluene or deuteriated
toluene, and a detailed vibrational analysis of the fluorescence spectra carried
out.57 The photodissociation dynamics of azulene at 193 nm have been studied
in a molecular beam using multimass ion-imaging techniques.58 Most of the
excited molecules produced at this wavelength relax rapidly to the electronic
ground state through internal conversion, then isomerize to naphthalene, and
eventually dissociate by H-atom elimination.
7.2 Photoeliminations from Organohalogen Compounds. – A review has been

published of the photobehaviour of alkyl, aryl, benzylic and homobenzylic
halides in solution and of alkyl halides in the gas phase.59
UV-induced dissociation of CD3Cl trapped inside thin amorphous solid
water layers on Ru(001) has been examined.60 Stable products, such as C2D6,
CHD3, CD3CD2Cl and CD3OH, were detected via post-irradiation desorption.
An investigation of the UV-induced photodecomposition of CHBr3 multilayers
on Cu/Ru(001) has been carried out.61 Methyl radicals accumulated on the
surface were the precursors for the formation of methane and ethene. A
photofragment translational spectroscopic study of the 248-nm photolysis of
methyl hypochlorite (CH3OCl) – a molecule that acts as an atmospheric
chlorine reservoir – has shown that the primary photodissociation channel is
cleavage of the O–Cl bond to produce Cl atoms and CH3Od radicals.62 The
results are in accord with previous theoretical and experimental findings, but
also suggest that CH3OCl could serve as a precursor of CH3Od radicals with
high and well-defined rotational and translational energies.
An experimental and theoretical study of the 355-nm photodissociation of
CH2Cl2 and CH2Br2 has shown that both molecules follow similar ionization
patterns, with H1, CH21, X1, CX1 and CH2X1 (X ¼ Cl, Br) as the major
ions.63 The proposed mechanism involves dissociation of CH2X2 into CH2X,
which then dissociates further by several competitive channels, the products of
Photochemistry, 36, 2007, 205–231 221
which are subsequently ionized. Dichloromethane molecules vibrationally ex-

cited to the second C–H stretch overtone have been photodissociated with light
of l ¼ B235 nm, and the Cl atoms produced were studied by resonantly
enhanced multiphoton ionization.64 The results suggest fast dissociation and
the involvement of several upper states of different symmetries, and also higher
non-adiabaticity for vibrationally excited than for vibrationless ground-state
molecules. The photochemistry of CH2I2 at 266 nm in acetonitrile solution has
been investigated by femtosecond and nanosecond laser photolysis.65 The
CH2I–I isomer was produced with a quantum yield of B70%. High isomer
quantum yields (470%) were also measured for n-hexane, dichloromethane,
methanol and ethanol solutions. The isomer is formed within B15 ps after
excitation, and survives for nanoseconds or microseconds before decaying by a
mixture of first- and second-order processes. The measured rate constants for n-
hexane solution correspond to intramolecular decomposition of CH2I–I to the
dCH I radical and an I atom, with the additional formation of I in MeCN.
2
The observation of H1 and I following UV photolysis of CH2I2 in water has
been reported.66 Since the concentrations of the two ions are about the same,
this suggests a reaction which produces HI as a leaving group. An ab initio
investigation was also carried out for the reaction between isodiiodomethane,
CH2I–I, and H2O, which showed how the CH2I–I could react with an O–H
bond by insertion and HI elimination, and that this process would be catalysed
by a second water molecule.
The rotational spectrum of HCBr produced by 193-nm photolysis of bromo-
form has been studied by kinetic microwave spectroscopy (420–472 GHz).67
Pulsed multiphoton photolysis of CHBr3 at 248 nm in the presence of excess O2
has led to the first observation of CO UV-visible chemiluminescence.68 The
luminescence is best accounted for by postulating reactions between O2 and
vibrationally excited methylidene radicals in two different electronic states:
CH(X2P) and CH(a4S). The photodissociation of CF3I at 248 nm has been
studied in a high-resolution photofragment translational spectrometer.69 Di-
chlorocarbene, CCl2, has been generated by 213-nm photolysis of CCl4, and the
kinetics of its reactions with C2H4, NO, N2O and halomethanes determined.70
The photodissociation dynamics of n-alkyl bromides, RBr (R ¼ Et, n-Pr, n-
Bu, n-pentyl), at B234 and 267 nm have been investigated using resonance
enhanced multiphoton ionization (REMPI) with time-of-flight mass spect-
rometry.71 Bromine atoms were produced by direct dissociation of the R–Br
bond, and in this wavelength range ground-state bromine was the major
product. A concerted three-body dissociation of CH2XCH2Y (X, Y ¼ Br,
Cl) into X þ Y þ C2H4 has been discovered by product translational spec-
troscopy following absorption of 193-nm photons.72 No stable CH2BrCH2 or
CH2ClCH2 was detected. Two theoretical studies of the of HCl elimination
from 193-nm photodissociation of vinyl chloride have been published, the first
using AM1 trajectory calculations with specific reaction parameters,73 and the
second a direct MP2/6-31G(d,p) classical trajectory approach.74 Broadly
speaking, the results were in good agreement, and support an earlier proposal
that three-centre elimination of HCl and isomerization of vinylidene to ethyne
222 Photochemistry, 36, 2007, 205–231
take place in a concerted, non-synchronous manner. In addition, the results

indicate that the four-centre channel produces rotationally hot HCl molecules,
while low rotational states of HCl derive from the three-centre channel, which
is at odds with a previous conclusion. Photodissociation of allyl-d2 iodide,
H2C¼CDCH2I at 193 nm and the dynamics of the resulting allyl-d2 radical
have been investigated by photofragment translational spectroscopy.75 A pre-
vious study had found the allyl radical stable at internal energies up to about 60
kJ mol1 higher than the barrier to allene þ H formation as the result of a
centrifugal barrier, and this new study shows that the allyl-d2 radical is stable to
allene þ D formation at energies of about 10 kJ mol1 higher than that of the
non-deuteriated analogue. This is thought to be the result of the difference in
zero-point energies and a reduction in the impact parameter of the fragments
due to the decrease in frequency of the C–D bending modes. A minor fraction
of the allyl-d2 radicals isomerize to the 2-propenyl radical, but the dominance of
the direct alleneþH(D) formation is in accord with previous conclusions.
Photolysis (300 nm) of the tricyclic molecule (72) (Scheme 13) generates
carbomethoxyfluorocarbene (73) and indan.76 Laser flash photolysis studies of
this reaction in solution, with UV-visible and IR detection, demonstrated that,
contrary to expectations, (73) is more reactive than its chloro analogue.
F CO2Me
hν F
+
O
(72) (73)
Scheme 13
A theoretical examination of the excited state properties of fluoro-, chloro-,

bromo- and iodobenzene using CASSCF and CASPT2 methods has been
carried out with the aim, amongst others, of understanding the experimental
observation that chloro- and bromobenzene each have one fast dissociation
channel, whereas iodobenzene has two.77 The computations indicate that the
dissociation channels for chloro- and bromobenzene and the slower iodoben-
zene dissociation channel are due to intersystem crossing from a bound (p,p*)
singlet excited state to a repulsive (n,s*) triplet excited state. The faster
iodobenzene dissociation channel involves direct dissociation of an antibonding
(n,s*) singlet excited state. Another theoretical study was concerned with the
ground states and several low-lying excited states of bromobenzene, o-, m- and
p-dibromobenzene and 1,3,5-tribromobenzene.78 Experimentally, it was known
that o- and m-dibromobenzene each have two ultrafast predissociation chan-
nels, while bromobenzene, p-dibromobenzene and 1,3,5-tribromobenzene each
have only one such channel. The calculated potential energy curves provide an
explanation, showing that the reduction of symmetry from C2v to Cs along the
main reaction coordinate, which occurs only in o- and m-dibromobenzene,
opens up a second predissociation channel.
Photochemistry, 36, 2007, 205–231 223
In an investigation of the photodissociation dynamics of fluorobenzene and

d5-fluorobenzene at 193 nm, it has been found that four-centre elimination of
HF or DF was the major dissociation channel, although small amounts of H-
or D-atom elimination were also observed.79 The photodissociation of bromo-
benzene at 267 and 234 nm has also been examined experimentally.80 The
branching ratio, Br(2P1/2)/Br(2P3/2), was found to be smaller than that for the
dissociation of 1-bromoheptane, indicating a different photodissociation mech-
anism for aryl and alkyl halides. In addition, the branching ratio for bromo-
benzene decreases with a decrease in excitation wavelength. The
photodissociation dynamics of o-, m- and p-bromotoluene at 270 nm have
been investigated by femtosecond pump-probe spectroscopy.81 The initially
excited S1 (p,p*) state is predissociative via either the repulsive 3(n,s*) state or
high vibrational levels of the S0 state. In the photodissociation of o-, m- and p-
chlorotoluene at 193 nm, photoreactions corresponding to ClC6H4CH3 -
ClC6H4CH2 þ H and ClC6H4CH3 - ClC6H4 þ CH3 are observed as well as
Cl-atom elimination.82 The photodecomposition of iodobenzene adsorbed on
the Mo2C/Mo(100) surface has been studied in the 100–1200 K temperature
range.83
7.3 Photofragmentations of Organosilicon Compounds. – There have been

several studies of the infrared multiphoton decomposition of silanes. Isotope-
selective IR multiphoton dissociation of difluorosilane was achieved with 977.2
cm1 light from a pulsed CO2 laser, the dissociation rate for 28SiH2F2 being
approximately twice as fast as for the other isotopomers (29SiH2F2 and
30
SiH2F2).84 It was estimated, however, that only a small proportion of the
molecules interact with the IR radiation, owing to a ‘rotational bottleneck’
effect; the dissociation is therefore very inefficient. IR multiphoton dissociation
of trichlorosilane molecules, irradiated by pulses from CO2 and NH3 lasers,
gives mainly HCl and a solid product, presumed to be (SiCl2)n, in yields which
depend on the laser frequency and the pressure of SiHCl3.85 In a related study,
the IR multiphoton dissociation of SiHCl3 was carried out in the presence of
scavenger gases, such as O2, CO2, OCS, halomethanes, BCl3 and TiCl4.86 In
some cases, stable volatile products were detected. At relatively high pressures
of SiHCl3 ( Z 400–800 Pa), its photolysis in mixtures with F-, Cl- or Br-
containing scavengers gave products of the type SiX4nCln (X ¼ F, Br; n ¼
1–4); a conversion into SiCl4 higher than 70% could be achieved. At low SiHCl3
pressures, however, a stable volatile product was observed only with BCl3, this
resulting from insertion of SiCl2 into the B–Cl bond. In the IR multiphoton
dissociation of diethylsilane unders collisionless conditions, dissociation of both
C–Si and C–C bonds were found as the main unimolecular processes.87
Photolysis of the silacyclopropenes (74: R ¼ Me, Et) at 254 nm in methyl-
cyclohexane glasses at 9–80 K led to the observation of a characteristic broad
EPR signal due to bis(tri-tert-butylsilyl)silylene, (tBu3Si)2Si:, the temperature
dependency of which established that the silylene has a triplet ground state.88
The identified products, which included the disilacyclobutane derivative (75)
and (tBu3Si)2SiH2, support this conclusion. The effects of ortho-methyl
224 Photochemistry, 36, 2007, 205–231
substitution on the reactivity of 1,1-diarylsilenes has been investigated by

photolytically generating five silenes (76: Ar1 ¼ Ar2 ¼ 2-MeC6H4; Ar1 ¼ Ph,
Ar2 ¼ 2,6-Me2C6H3; Ar1 ¼ Ph, Ar2 ¼ 2,4,6-Me3C6H2; Ar1 ¼ 2-MeC6H4, 2,6-
Me2C6H3; Ar1 ¼ Ar2 ¼ 2,6-Me2C6H3) from the corresponding 1,1-diary-
lsilacylobutanes (77).89 UV absorption spectra and lifetimes of the silenes
(76) were determined in MeCN and hexane solution, along with the absolute
rate constants for their reactions with MeOH and AcOH; rates were found to
vary over 3–4 orders of magnitude. Photolysis of the silacyclobutane (78) gave
three isomeric products, derived from intramolecular trapping of a biradical
intermediate, as well as the expected ether-stabilized silene (79).90 Recent
advances in the silylation of fullerenes by active species – silylenenes and silyl
radicals – generated by photolysis of polysilane have been summarized.91
H
But3Si SiBut3 But3Si Si
Si
But2Si Me
R R Me
(74) (75)
Ar1 Ar1
Si CH2 Ar2 Si
Ar2
(76) (77)
OMe
CH2OMe
Ph Si Si CH2
Ph
(78) (79)
7.4 Photofragmentations of Organosulfur Compounds. – The gas-phase Ra-

man spectra of cyanogen isothiocyanate (NCNCS) and its photolysis product,
isocyanogen (CNCN), have been detected in a study of the 266 nm photodis-
sociation of NCNCS.92 Direct C–S bond cleavage appears to be the most likely
pathway for the formation of CNCN.
UV-irradiation of the 4-(2-halobenzyl)-1,2,4-triazole-3-thiones (80) under
basic conditions gave ring-closed benzothiazines (81) and desulfurized triazoles
(82) (Scheme 14).93 Typical yields are given in the scheme. Apart from the two
o-chlorophenyl derivatives (80f,g), ring closure predominated. On the other
hand, benzophenone photosensitization gave exclusively desulfurized triazoles.
The results suggest that ring closure occurs via a singlet excited state and
desulfurization via a triplet excited state.
Photochemistry, 36, 2007, 205–231 225
R
N
R R
N N
N 254 nm N
N NH + N N
MeCN, H2O, 2M NaOH S
X S X
(80) (81) (82)
R X % %
a Ph Cl 41 10
b 4-MeC6H4 Cl 47 8
c 4-MeOC6H4 Cl 38 15
d 2-MeC6H4 Br 50 0
e PhCH2 Cl 45 0
f 2-ClC6H4 Cl 0 47
g 2-ClC6H4 Br 0 48
Scheme 14
7.5 Photolysis of o-Nitrobenzyl Derivatives and Related Compounds. – Time-

resolved FTIR monitoring of the flash photolysis of several 1-(2-nitrophe-
nyl)ethyl ethers (83) (Scheme 15) have shown that two parallel pathways are
involved, but that release of the alcohol (89) is rate-limited by the decompo-
sition of a common hemiacetal intermediate (88).94 The two pathways are
(i) direct formation of the hemiacetal (88) from the initially generated aci-nitro
species (84) (the curly arrows shown in (84) refer to this process) and
(ii) formation of the bicyclic intermediate (87) via proton transfer. One of
the compounds (83d) was studied in greater detail by time-resolved FTIR and
UV-visible spectrosocopy, and by product studies. The latter confirmed clean
photolytic decomposition to the alcohol (89d) as well as the by-product (90).
Computations suggest that the pKa of (84) is likely to determine the partition
between the two pathways. Although this reaction scheme seems to be general
for 1-(2-nitrophenyl)ethyl ethers, it contrasts with results for the related
2-nitrobenzyl ether (91), which photolysed without the involvement of a
long-lived hemiacetal.
Wavelength dependent differential release of compounds from a solid-phase
resin has been demonstrated, using beads bifurcated with nitroveratryl (92) and
pivaloyl glycol (93) photo-linkers.95 A narrow bandwidth tuneable pulsed laser
was used for photolysis, and it was found that the nitroveratryl linker under-
goes cleavage over a wide range of wavelengths, with maximum cleavage rates
at 320 and 340 nm. On the other hand, the pivaloyl glycol linker is photo-stable
at wavelengths above 340 nm. 6-Nitroveratryloxycarbonyl chloride (94) has
been used to protect amino groups, allowing selective labelling of peptides in
solution.96 The photolabile protecting groups are easily removed after the
labelling reaction. This technique is claimed to offer the advantages of solid-
phase synthesis combined with the flexibility of labelling reactions in solution,
226 Photochemistry, 36, 2007, 205–231
Me R Me R Me R Me R
+ +
O hν O −H O +H O
OH +H+ O− −H+ O−
NO2 N N N
−
O O− OH
(83) (84) (85) (86)
−OH
Me
Me O H Me O R
O O R
+ RCH2OH O
NO NO N
OH
(90) (89) (88) (87)
a: R = CO2− O CO2−
b: R = CH2N+Me3
c: R = CH2OPO32− NO2
d: R = CH2OP(OMe)O2−
(91)
Scheme 15
thus permitting selective labelling of nanomole amounts. This work has also
been the subject of a patent.97
O
O
OTMS
O NO2
HO O
OH O OTBDMS
MeO HO
(92) (93)
The 2-(2-nitrophenyl)propyloxycarbonyl group has been applied as a pho-

tolabile amino protecting group for amino acids to be used as building blocks in
photolithographic solid-phase peptide synthesis.98 The protected amino acids
(95) are cleaved by UV radiation about twice as fast as the corresponding 2-
nitroveratryloxycarbonyl-protected analogues. A 2-mercapto-1-(2-nitrophe-
nyl)ethylamine moiety has been used as photoremovable ligation auxiliary in
polypeptide synthesis.99
MeO O
O NO2
O CO2H
MeO Cl
O N R
H
NO2
(94) (95)
Photochemistry, 36, 2007, 205–231 227
7.6 Other Photofragmentations. – The 193.3 nm photodynamics of propan-1-

ol and propan-2-ol and their partially deuteriated isotopomers have been
investigated using the high-n Rydberg-atom time-of-flight technique.100 The
results show that O–H bond fission is the primary H-atom production channel
in both cases. Indeed, the photodissociations of these two molecules are nearly
identical and similar to those of methanol and ethanol, suggesting a common
RO–H dissociation mechanism: after the nO - s*(O–H) excitation, localized
on the H–O–C moiety, the H atom is ejected promptly in the H–O–C plane in a
time scale shorter than a rotational period of the parent molecule.
In the light of the fact that dimethyl ether has been identified in the
interstellar gas in cold molecular clouds, the vacuum-UV photodissociation
of this compound has been studied at 10 K in Ar and N2 matrices, in the solid
phase and in amorphous water ice.101 The primary photoproducts were iden-
tified by FTIR spectroscopy as formaldehyde and methane, which are both
produced via two channels without subsequent reactions with water ice. The
193.3 nm photodissociation dynamics of ethyl ethynyl ether have been exam-
ined by photofragment translational spectroscopy and laser-induced fluores-
cence.102 Only cleavage of the ethynyl–O bond to form HCRCOd and an ethyl
radical occurred. Neither cleavage of the other C–O bond nor molecular
elimination to give C2H4 þ CH2CO was observed. As was briefly mentioned
previously in Section 5, the H-atom production channel in the 193–215 nm
photodissociation of ketene has been studied both experimentally and theoret-
ically.32,33 The observed product energy disposal was interpreted on the basis of
one-photon absorption to the 1B1 electronic excited state, followed by internal
conversion to high vibrational levels of the electronic ground state and subse-
quent unimolecular decay to H þ HCCO.
Bhc-diol (6-Bromo-4-(1,2-dihydroxyethyl)-7-hydroxycoumarin) (97) can be
used under simulated physiological conditions as a photolabile protecting
group for aldehydes and ketones.103 The photo-induced deprotection reaction
is shown in Scheme 16, where the protected carbonyl compound, R1COR2, is
released from the caged precursor (96). An advantage of this method of
protection is that the Bhc-diol can be removed either with UV light (350
nm), by one-photon absorption, or with 740 nm light, by two-photon absorp-
tion. The latter procedure has the obvious advantage of not exposing
R2
1
R O OH
O HO
Br 1- or 2-photon Br
excitation O
+
−O O O −O O O R1 R2
(96) (97)
Scheme 16
228 Photochemistry, 36, 2007, 205–231
potentially delicate molecules to UV radiation, and has been demonstrated

for the photo-release of benzaldehyde, piperonal, acetophenone and cyclo-
hexanone.
Classical trajectory studies have been carried out for the photodissociation of
sym-triazine for energies equivalent to 193, 248, 266, 285 and 295 nm excita-
tion.104 The calculated average translational and rotational energies of the
HCN molecules produced are in good agreement with some experimental
results. Moreover, the calculated shapes of the translational energy distribu-
tions are also in good agreement with experiment, at least for the lower
energies, though somewhat narrower than the experimental distributions at
higher energies.
References
1. W. Horspool and F. Lenci (ed.), CRC Handbook of Photochemistry and
Photobiology, 2nd edn., CRC Press, Boca Raton, Florida, 2004.
2. I. R. Dunkin, in CRC Handbook of Organic Photochemistry and Photobiology, 2nd
edn., W. Horspool and F. Lenci (ed), CRC Press, Boca Raton, Florida, 2004, Chp.
15, pp. 14/1–14/27.
3. I.R. Dunkin, in CRC Handbook of Organic Photochemistry and Photobiology, 2nd
edn., W. Horspool and F. Lenci (ed.), CRC Press, Boca Ratoon, Florida, Chp. 15,
2004, pp. 15/1–15/23.
4. R.S. Givens, P.G. Conrad II, A.L. Yousef and J.-I. Lee, in CRC Handbook of
Photochemistry and Photobiology, 2nd edn., W. Horspool and F. Lenci (ed.), CRC
Press, Boca Raton, Florida, Chp. 69, 2004, pp. 69/1–69/46.
5. B.A. Thrush, Photochem. Photobiol. Sci., 2003, 2, 453–454.
6. M.W. Windsor, Photochem. Photobiol. Sci., 2003, 2, 455–458.
7. A.A. Popov and A.I. Burshtein, J. Phys. Chem. A., 2003, 107, 9688–9694.
8. W. Adam and A.V. Trofimov, in CRC Handbook of Photochemistry and
Photobiology, 2nd edn., W. Horspool and F. Lenci (ed.), CRC Press, Boca Raton,
Florida, 2004, Chp. 93, pp. 93/1–93/16.
9. A. Sinicropi, C.S. Page, W. Adam and M. Olivucci, J. Am. Chem. Soc., 2003, 125,
10947–10959.
10. W. Adam, M.C. Sajimon and A.V. Trofimov, Photochem. Photobiol. Sci., 2003, 2,
677–680.
11. T.C. Celius and J.P. Toscano, in CRC Handbook of Organic Photochemistry and
Photobiology, 2nd edn., W. Horspool and F. Lenci (ed.), CRC Press, Boca Raton
Florida, 2004, Chp. 92, pp. 92/1–92/10.
12. J.-M. Fedé, S. Jockusch, N. Lin, R.A. Moss and N.J. Turro, Org. Lett., 2003, 5,
5027–5030.
13. T. Itoh, K. Hirai and H. Tomioka, J. Am. Chem. Soc., 2004, 126, 1130–1140.
14. R. Bonneau, D. Collado and M. T.H. Liu, J. Photochem. Photobiol. A, 2003, 161,
43–50.
15. P. Bednarek and C. Wentrup, J. Am. Chem. Soc., 2003, 125, 9083–9089.
16. E. Okada, Y. Komazawa, M. Kurihara, H. Inoue, N. Miyata, H. Okuda,
T. Tsuchiya and Y. Yamakoshi, Tetrahedron Lett., 2004, 45, 527–529.
17. M. Kurono, A. Shimomura and M. Isobe, Tetrahedron, 2004, 60, 1773–1780.
Photochemistry, 36, 2007, 205–231 229
18. T.C. Celius, Y. Wang and J.P. Toscano, in CRC Handbook of Organic Photo-
chemistry and Photobiology, 2nd edn., W. Horspool and F. Lenci (ed.), CRC Press,
Boca Raton Florida, 2004, Chp. 90, pp. 90/1–90/16.
19. P. Haiss and K.-P. Zeller, Z. Naturforsch. B, 2003, 58, 595–605.
20. P. Haiss and K.-P. Zeller, Org. Biomol. Chem., 2003, 1, 2556–2558.
21. A. Bogdanova and V.V. Popik, J. Am. Chem. Soc., 2003, 125, 14153–14162.
22. G. Bucher, A. Strehl and W. Sander, Eur. J. Org. Chem., 2003, 2153–2158.
23. G. Bucher, in CRC Handbook of Organic Photochemistry and Photobiology, 2nd
edn., W. Horspool and F. Lenci, (ed), CRC Press, Boca Raton, Florida, 2004, Chp.
46, pp. 46/1–46/19.
24. E. Leyva, R. Sagredo and E. Moctezuma, J. Fluorine Chem., 2004, 125, 741–747.
25. A.V. Budruev, L.N. Karyakina and A.V. Oleinik, High Energy Chem., 2004, 38,
20–24.
26. C. Tönshoff and G. Bucher, Eur. J. Org. Chem., 2004, 269–271.
27. H. Tomioka and S. Sawai, Org. Biomol. Chem., 2003, 1, 4441–4450.
28. S.V. Chapyshev and H. Tomioka, Bull. Chem. Soc. Jpn., 2003, 76, 2075–2089.
29. S.V. Zelentsov, M.V. Kuznetsov and N.V. Zelentsova, Russ. Chem. Bull., 2003, 52,
1296–1300.
30. T. Sato, A. Narazaki, Y. Kawaguchi, H. Niino and G. Bucher, Angew. Chem. Int.
Ed., 2003, 42, 5206–5209.
31. T. Sato, A. Narazaki, Y. Kawaguchi, H. Niino, G. Bucher, D. Grote, J.J. Wolff,
H.H. Wenk and W. Sander, J. Am. Chem. Soc., 2004, 126, 7846–7852.
32. J.P. Cole and G.G. Balint-Kurti, J. Chem. Phys., 2003, 119, 6003–6016.
33. E.J. Feltham, R.H. Qadiri, E.H. Cottrill, P.A. Cook, J.P. Cole, G.G. Balint-Kurti
and M.N.R. Ashfold, J. Chem. Phys., 2003, 119, 6017–6031.
34. M. Saldyka and Z. Mielke, Phys. Chem. Chem. Phys., 2003, 5, 4790–4797.
35. S. Breda, I. Reva, L. Lapinski and R. Fausto, Phys. Chem. Chem. Phys., 2004, 6,
929–937.
36. S. Breda, L. Lapinski, I. Reva and R. Fausto, J. Photochem. Photobiol. A, 2004,
162, 139–151.
37. M. Laferrière, C.N. Sanramé and J.C. Scaiano, Org. Lett., 2004, 6, 873–875.
38. M. Oelgemöller, P. Cygon, J. Lex and A.G. Griesbeck, Heterocycles, 2003, 59,
669–684.
39. B. Abel, J. Assmann, P. Botschwina, M. Buback, M. Kling, R. Oswald,
S. Schmatz, J. Schroeder and T. Witte, J. Phys. Chem. A, 2003, 107, 5157–5167.
40. B. Abel, J. Aßmann, M. Buback, M. Kling, S. Schmatz and J. Schroeder, Angew.
Chem., Int. Ed., 2003, 42, 299–303.
41. J.E. Cortes-Figueroa, J. Chem. Educ., 2003, 80, 799–800.
42. R. Krishnan, H.E. Gottlieb and R.H. Schultz, Angew. Chem., Int. Ed., 2003, 42,
2179–2181.
43. V. Lehtovuori, J. Aumanen, P. Myllyperkiö, M. Rini, E.T.J. Nibbering and
J. Korppi-Tommola, J. Phys. Chem. A, 2004, 108, 1644–1649.
44. S. Sert, A. Ercag, O.S. Sentürk, B.T. Sterenberg, K.A. Udachin, Ü. Özdemir and
F.U. Sarikahya, Polyhedron, 2003, 22, 1689–1693.
45. O.S. Rentürk, H.A. Shekhel, B.T. Sterenberg, K.A. Udachin, S. Sert, Ü. Özdemir
and F.U. Sarikahya, Polyhedron, 2003, 22, 1659–1664.
46. E. Subasi, F. Ugur and O.S. Sentuerk, Transition Met. Chem., 2004, 29, 16–18.
47. M. El-Khateeb, A. Lataifeh and I. Jibril, Transition Met. Chem., 2003, 28, 85–87.
48. A. Aballay, F. Godoy, G.E. Buono-Core, A.H. Klahn, B. Oelckers, M.T. Garland
and J.C. Muñoz, J. Organomet. Chem., 2003, 688, 168–173.
230 Photochemistry, 36, 2007, 205–231
49. J.F. Arenas, J.C. Otero, D. Peláez and J. Soto, J. Chem. Phys., 2003, 119, 7814–7823.
50. T.J. Oberhuber, U. Kensy and B. Dick, Phys. Chem. Chem. Phys., 2003, 5,
2799–2806.
51. C.M. Pavlos, A.D. Cohen, R.A. D’Sa, R.B. Sunoj, W. Wasylenko, P. Kapur,
H. A. Relyea, N.A. Kumar, C.M. Hadad and J.P. Toscano, J. Am. Chem. Soc.,
2003, 125, 14934–14940.
52. J. O’Reilly, S. Douin, S. Boyé, N. Shafizadeh and D. Gauyacq, J. Chem. Phys.,
2003, 119, 820–826.
53. Y. Ganot, A. Golan, X. Sheng, S. Rosenwaks and I. Bar, Phys. Chem. Chem.
Phys., 2003, 5, 5399–5404.
54. L. Khriachtchev, H. Tanskanen, A. Cohen, R.B. Gerber, J. Lundell, M. Pettersson,
H. Kiljunen and M. Räsänen, J. Am. Chem. Soc., 2003, 125, 6876–6877.
55. S.-H. Lee, Y.-Y. Lee, Y.T. Lee and X. Yang, J. Chem. Phys., 2003, 119, 827–838.
56. S.-H. Lee, Y.T. Lee and X. Yang, J. Chem. Phys., 2004, 120, 10992–10999.
57. K. Uejoh, Spectrochim. Acta, Part A., 2004, 60, 595–602.
58. M.-F. Lin, C.-L. Huang, Y.T. Lee and C.-K. Ni, J. Chem. Phys., 2003, 119,
2032–2036.
59. P. J. Kropp, in CRC Handbook of Organic Photochemistry and Photobiology, 2nd
edn., W. Horspool and F. Lenci, (ed), CRC Press, Boca Raton, Florida, 2004, Chp.
1, pp. 1/1–1/32.
60. Y. Lilach and M. Asscher, J. Chem. Phys., 2003, 119, 407–412.
61. T. Livneh and M. Asscher, J. Phys. Chem. B, 2003, 107, 11382–11390.
62. M.J. Krisch, L.R. McCunn, K. Takematsu, L.J. Butler, F.R. Blase and J. Shu,
J. Phys. Chem. A, 2004, 108, 1650–1656.
63. P. Sharma, R.K. Vatsa, D.K. Maity and S.K. Kulshreshtha, Chem. Phys. Lett.,
2003, 382, 637–643.
64. R. Marom, A. Golan, S. Rosenwaks and I. Bar, Chem. Phys. Lett., 2003, 378,
305–312.
65. A.N. Tarnovsky, V. Sundström, E. Åkesson and T. Pascher, J. Phys. Chem. A.,
2004, 108, 237–249.
66. Y.-L. Li, C. Zhao, W.M. Kwok, X. Guan, P. Zuo and D.L. Phillips, J. Chem.
Phys., 2003, 119, 4671–4681.
67. C. Duan, M. Hassouna, A. Walters, M. Godon, P. Dréan and M. Bogey, J. Mol.
Spectrosc., 2003, 220, 113–121.
68. G.L. Vaghjiani, J. Chem. Phys., 2003, 119, 5388–5396.
69. X. Wang, Z. Tian, T. Shi, X. Shi, D. Yang and Q. Zhu, Chem. Phys. Lett., 2003,
380, 600–603.
70. Y. Liu, Y. Xin, L. Pei, Y. Chen and C. Chen, Chem. Phys. Lett., 2004, 385,
314–318.
71. R. Zhu, B. Tang, L. Ji, Y. Tang, S. Zhang and B. Zhang, Opt. Commun., 2004, 235,
325–331.
72. Y.-R. Lee, C.-C. Chen and S.-M. Lin, J. Chem. Phys., 2004, 120, 1223–1230.
73. E. Martinez Núñez, A. Fernández-Ramos, S.A. Vázquez, F. J. Aoiz and L. Bañares,
J. Phys. Chem. A., 2003, 107, 7611–7618.
74. E. Martı́nez-Núñez, S.A. Vázquez, F.J. Aoiz, L. Bañares and J.F. Castillo, Chem.
Phys. Lett., 2004, 386, 225–232.
75. D.E. Szpunar, Y. Liu, M.J. McCullagh, L.J. Butler and J. Shu, J. Chem. Phys.,
2003, 119, 5078–5084.
76. E.M. Tippmann, G. Holinga and M. S. Platz, Org. Lett., 2003, 5, 4919–4922.
77. Y.-J. Liu, P. Persson and S. Lunell, J. Phys. Chem. A., 2004, 108, 2339–2345.
Photochemistry, 36, 2007, 205–231 231
78. Y.-J. Liu, P. Persson, H.O. Karlsson, S. Lunell, M. Kadi, D. Karlsson and
J. Davidsson, J. Chem. Phys., 2004, 120, 6502–6509.
79. C.-L. Huang, J.-C. Jiang, A.M. Mebel, Y.T. Lee and C.-K. Ni, J. Am. Chem. Soc.,
2003, 125, 9814–9820.
80. B. Tang, R. Zhu, Y. Tang, L. Ji and B. Zhang, Chem. Phys. Lett., 2003, 381, 617–622.
81. M. Kadi, E. Ivarsson and J. Davidsson, Chem. Phys. Lett., 2004, 384, 35–39.
82. M.-F. Lin, C.-L. Huang, V. V. Kislov, A. M. Mebel, Y. T. Lee and C.-K. Ni,
J. Chem. Phys., 2003, 119, 7701–7704.
83. L. Bugyi, A. Oszkó and F. Solymosi, Surf. Sci., 2003, 539, 1–13.
84. S.R. Gorelik, E.N. Chesnokov, A.V. Kuibida, R.R. Akberdin and A.K. Petrov,
Appl. Phys. B, 2004, 78, 119–125.
85. V.M. Apatin, V.B. Laptev and E.A. Ryabov, Quantum Electron., 2003, 33, 894–896.
86. V.M. Apatin, V.B. Laptev and E.A. Ryabov, High Energy Chem., 2003, 37, 272–278.
87. G.P. Zhitneva and Y. N. Zhitnev, High Energy Chem., 2004, 38, 184–190.
88. A. Sekiguchi, T. Tanaka, M. Ichinohe, K. Akiyama and S. Tero-Kubota, J. Am.
Chem. Soc., 2003, 125, 4962–4963.
89. T.R. Owens, C.R. Harrington, T.C.S. Pace and W.J. Leigh, Organometallics, 2003,
22, 5518–5525.
90. W.J. Leigh and X. Li, J. Am. Chem. Soc., 2003, 125, 8096–8097.
91. T. Wakahara, Y. Maeda, M. Kako, T. Akasaka, K. Kobayashi and S. Nagase,
J. Organomet. Chem., 2003, 685, 177–188.
92. P. Li, L.K. Wong and W.Y. Fan, Chem. Phys. Lett., 2003, 380, 117–122.
93. A. Senthilvelan, D. Thirumalai and V.T. Ramakrishnan, Tetrahedron, 2004, 60,
851–860.
94. J.E.T. Corrie, A. Barth, V.R.N. Munasinghe, D.R. Trentham and M.C. Hutter,
J. Am. Chem. Soc., 2003, 125, 8546–8554.
95. M. Ladlow, C.H. Legge, T. Neudeck, A.J. Pipe, T. Sheppard and L.L. Yang,
Chem. Commun., 2003, 2048–2049.
96. N. Koglin, M. Lang, R. Rennert and A.G. Beck-Sickinger, J. Med. Chem., 2003,
46, 4369–4372.
97. N. Koglin, M. Lang and A.G. Beck-Sickinger (Universität Leipzig, Germany),
German Patent DE 10,334,499, 12 Feb 2004; Chem. Abstr., 2004, 140, 164240.
98. K.R. Bhushan, C. DeLisi and R.A. Laursen, Tetrahedron Lett., 2003, 44, 8585–8588.
99. T. Kawakami and S. Aimoto, Tetrahedron Lett., 2003, 44, 6059–6061.
100. W. Zhou, Y. Yuan and J. Zhang, J. Chem. Phys., 2003, 119, 7179–7187.
101. A. Schriver, J.M. Coanga, L. Schriver-Mazzuoli and P. Ehrenfreund, Chem. Phys.
Lett., 2004, 386, 377–383.
102. M.J. Krisch, J.L. Miller, L.J. Butler, H. Su, R. Bersohn and J. Shu, J. Chem. Phys.,
2003, 119, 176–186.
103. M. Lu, O.D. Fedoryak, B.R. Moister and T.M. Dore, Org. Lett., 2003, 5, 2119–2122.
104. J. Lee, E. Dong, D. Jin, K. Song and M.A. Collins, Phys. Chem. Chem. Phys.,
2004, 6, 945–948.
Polymer Photochemistry
BY NORMAN S. ALLEN
Department of Chemistry, Manchester Metrapolitan University, Chester
Street, Manchester, M1 5GD
1 Introduction
The field of polymer photochemistry continues to be recognized as an active

area in applied photochemistry, with many topics growing in industrial devel-
opment. Photopolymerization and photocuring science and technologies are
being developed particularly with regard toward designing novel and specific
initiators and materials for specialist applications. Interest in active ionic
initiators and radical-ionic processes remains a high priority, while the photo-
crosslinking of polymers is attractive in terms of enhancing the physical and
mechanical properties of electronic materials and the development of liquid
crystalline materials. The optical properties of polymers remains an active area
of strong development with a continued growth in photochromic and liquid
crystalline materials. Last year saw the first ever literature explosion in LEDs
(light emitting diodes). In this year’s review it represents one of the largest
specialized topics in photochemistry and photophysics.
The photooxidation of polymers on the other hand continues to remain at a
low profile. Bio- and photodegradable plastics continue to be useful for
agricultural usage, although interest here is again minimal. The same applies
to polymer photostabilization, where commercial applications dominate very
much, with emphasis on the practical use of stabilizers. For dyes and pigments,
stability continues to be a major issue in so far as this section is concerned.
2 Photopolymerization
A number of reviews have appeared on the function of different types of

photoinitiators and their future development and applications.1–3 A number of
articles have targeted interest in photosensitive polyelectrolyte diazo systems,4
pressure-sensitive adhesives and coatings,5,6 bonding of epoxy resins,7 elec-
trodeposition materials,8 heat transfer in thick films,9 ring-opening metathesis10
and curing for microelectronics.11
232
Photochemistry, 36, 2007, 232–298 233
2.1 Photoinitiated Addition Polymerization. – Many new photoinitiator systems

continue to be developed for photopolymerization. Novel macroinitiators based
on thioxanthone have been developed and found to be highly efficient when bound
to a polymer chain and used in conjunction with a free amine cosynergist.12 Here
the polymer chain was found to influence the reactivity of the alkylamino radicals
and not the excited state reactivities of the initiator molecule. In a study on a series
of 2-substituted thioxanthones in the presence of diethyldiethanolamine, it has
been shown that photoinitiation efficiency is dependent upon the electron-with-
drawing efficiency of the substituent.13 Here the singlet state of the initiator was
found to be deactivated by the amine, with a rate constant near the diffusion
controlled limit, and evidence of strong ketone-amine complexation. In another
study on a thioxanthone-amine interaction with acrylic acid polymerization, the
propagation rate was found to be linear with monomer concentration.14 In
another study using 2-chlorothioxanthone as the initiator, the structure of the
amine cosynergist has been found to be important in the photopolymerization of
methyl methacrylate (MMA).15 So hydroxyl substituted alkylamines were found
to be more reactive than simple alkylamines, while dimethylanilines with elec-
tronacceptor groups in the 4-position were more efficient than those with electron-
donor groups. Ketone-amine complexation was again found to be highly
important in the overall reaction. Block copolymers of MMA and styrene with
hydroxyl terminal groups have been made using an alkanolamine as a co-synergist
with benzophenone as initiator.16 These end groups were then subsequently mod-
ified into bromine groups via esterification with 2-bromopropionyl bromide. These
block copolymers were also found to exhibit living radical characteristics. Similar
work on MMA polymerization using benzoquinones as initiator found that the
steric hindrance of substituents on the ring played a crucial role in initiation
activity.17 Propagation rate constants have been found not to be available in the
355 nm laser pulsed irradiation of N-vinylcarbazole.18 It was found that, even in
the presence of a free radical acetophenone-based initiator, radicals or cations
produced directly from the monomer were also responsible for the polymerization.
Using a mixture of cerous salts and an aminoethylene phosphonic acid as an
initiator, the photopolymerization of various acrylic and styrenic monomers gave
polymers of decreasing molecular weight with increasing initiator concentration.19
Solvent type has been found to influence the complexation and triplet-state activity
in the photopolymerization of 2-oxyethylmethacrylate and polyvinylpyrrolidone,20
while novel organic azides have been synthesized and found to be effective
photoinitiators of the polymerization of MMA.21 Diazides were found to be more
photoreactive than monoazides, both giving a dark reaction. Also, the azide group
was found to be reactive only when substituted onto an aromatic carbonyl
chromophore. Photocopolymer formation with L-lysine hydrochloride has been
found to be optimal in dioxane,22 while bis(trichloromethyl)-1,3,5-triazine has been
found to synergize effectively in the dye-amine photopolymerization of acrylic
monomers.23 This enhanced effect was found to be due to the radical inhibitor
scavenging ability of the triazine molecule. Phenylsilanes have also been found to
enhance the photopolymerization of MMA, giving rise to silyl terminated chains,24
whereas ethylene has been successfully photopolymerized over a chromium doped
234 Photochemistry, 36, 2007, 232–298
sieve.25 Here mesoporous sieves were found to be superior to those of silicalite

zeolites. Photoinitiator end-labelled polystyrenes have been prepared and investi-
gated as photoinitiators,26,27 as have novel terephthaloylbis(phosphonates)28 and
poly(caprolactones).29 In the latter case, hydroxyl functionalized benzoin ethers
were grafted to the polymer chains. Benzoyl species have also been found attached
to MMA chains,30 while N-alkoxypyridinium salts have been found to give alkoxy
radicals via cleavage of N–O bonds on irradiation.31 Using dyes as sensitizers, their
reduction potential has been found to be related to initiation efficiency. Rates of
electron-transfer processes have been measured between dyes and borate anions
using picosecond photolysis.32 Here the data indicated that the rate of electron
transfer and the free energy for reaction in polymerization displayed typical
‘normal Marcus region’ kinetic behaviour, indicating that the rate is a function
of the free energy change of electron transfer. Macroazo initiators have been
bound to polyethylene glycol chains and used to polymerize 2-hydroxyethyl
methacrylate,33 while a well defined polystyrene has been prepared through the
photoinduced properties of a 2-phenylacetophenone-ferric tri(N,N-diethyldithio-
carbamate).34 A novel ethereal monomer N-(p-phenoxyphenyl)methacrylamide
has been found to undergo electron transfer with other electron deficient acrylic
monomers inducing their polymerization,35 whereas poly(vinyl alcohol) has been
made as a product of the photoinduced emulsion polymerization of vinyl acetate.36
The photolysis of tetrasubstituted bi(phosphine sulfides) has been found to give
disubstituted thiophosphinyl radicals capable of initiating the photopolymeriza-
tion of MMA.37 Regiospecific polymers were obtained by this method with
phosphorus containing chain ends. Tetraalkylammonium salts undergo an intra-
molecular electron-transfer process upon irradiation, to give a radical ion pair that
will initiate polymerization of vinyl monomers.38 Monomer concentration was
found to be crucial in this regard, with higher concentrations giving rise to an
anion generated process, while at low concentrations a radical process is operative.
The photoinduced polymerization of acrylic monomers using dyes in a protein
restricted medium has been reported, where it was found that the dye photophysics
is altered when bound to the photopolymer.39 Here the dye-protein combination
was found to be crucial. Photo-Fenton reagents have been used to polymerize N-
vinylpyrrolidone,40 and thin films of fullerene have been photopolymerized with
254 nm light.41
Cationic processes remain high on the list. Diaryliodonium salts continue to
be attractive in this regard. In one study, the encapsulation of diaryliodonium
salts into montmorillonite allowed the formation of nanobubbles upon irradi-
ation in solutions containing tert-butyl methacrylate.42 Here butene and acrylic
acid products were formed due to photocleavage processes, the former being
trapped in the matrix causing expansion. Under visible light, oxiranes have
been found to undergo ring opening reactions via the same initiator,43 as have
dioxolanes.44 The initiators are also photosensitized by the presence of elec-
tron-transfer polynuclear aromatics with hydroymethyl groups,45 other hetero-
cyclics46 and titanocene.47 Propagation rate constants have been measured in
the cationic polymerization of cyclic acetals,48 while in the dual radical and
cationic initiation of the polymerization of THF the rate curve displayed both
Photochemistry, 36, 2007, 232–298 235
independent processes.49 Using a thioxanthone and a triphenylsulfonium salt,

electron transfer was observed from the former to the latter. Similar photos-
ensitization processes have also been observed using a benzoin ether,50 but in
this case the hydroxyl benzyl radicals were oxidized by the onium salts to give
cationic species. Triarylamine sulfonium salts with near-UV sensitivity have
been prepared where photoacid generation was found to be independent of the
counterion,51 while the living nature of THF polymerization by dip-
henyliodonium hexafluorophosphate has been associated with the stability of
the cationic species due to ion-pair formation with a less nucleophilic complex
metal halide anion.52 The radical and cationic polymerizations of 2-(N,N-
dimethylthiocarbamoyl)ethyl vinyl ether have been found to give low and high
molecular weight polymers respectively53 in good yields, whereas novel bicon-
tinuous microemulsions for cationic polymerization of MMA have been
developed utilizing ruthenium tris(4,7-diphenyl-1,10-pheanthroline)dichloride
with a surfactant acryloyloxyundecyltrimethylammonium chloride.54 For other
ruthenium complexes based on tris(2,2 0 -bipyridine), the most effective amine
co-synergists for acrylamide polymerization were found to be those that
quenched the complex fluorescence the most effectively.55 Here electron trans-
fer from the complex to the amine gives rise to a radical anion. Other studies of
interest include polymerizations via onium borates,56 cyclohexene oxide by N-
phenacyl-N,N-dimethylanilinium hexafluoroantimonate,57,58 oxiranes via allyl
ammonium salts with benzophenone moieties,59 the novel iodonium tetra-
kis(pentafluorophenyl)gallate,60 carbazolyl and phenothiazinyl thiiranes via
iodonium fluoroborates,61 propenyl ether and epoxy functionalized siloxanes
as hydrogen donors,62 reactivity of 1-propenyl vinyl ether systems63 and
aliphatic diepoxides via FeBF4 complexes.64
The inclusion of poly(3,4-epoxybut-1-ene) into photopolymerizing systems has
been found to exhibit a number of beneficial effects.65 It behaves as an effective
hydrogen donor and chain-transfer agent, as well as undergoing oxidation thus
inhibiting oxygen quenching effects. Vinyl ethers have also been found to
enhance the polymerization of dicycloaliphatic epoxides.66 It is also shown that
maleimide-vinyl ether combinations will photopolymerize, with the need for an
initiator. A number of workers have investigated the photoinduced polymeriza-
tion of C60. In C60 crystals under high pressure, tunneling processes have been
observed,67 whereas a simultaneous deposition and irradiation process has also
been found to be successful.68 The adiabatic and energy-transfer processes in
photogenerated excitons in C60 crystals have also been investigated.69 In single
crystals, structural defects were found to exist even at low temperatures. On a
different subject, nanowires of polydiacetylene have been prepared by the chain
polymerization of the monomers onto graphite surfaces.70 Morphological
changes in this type of polymer have also shown the formation of nodules in
addition to rod-like polymer crystallites with smooth surfaces.71
The photoinduced polymerization of 3-alkylated-2-pyrrolidones has been
found to increase with substitution on the pyrrolidone ring system,72 while
vinylidene fluoride (VDF) in the presence of hydrogen peroxide gives telechelic
PVDF through the formation of hydroxyl radicals, which can react with the
236 Photochemistry, 36, 2007, 232–298
fluorine sites to give carboxyl end groups.73 The photoinduced polymerization

of vinyl acetate has been found to depend upon the type of initiator and
temperature,74 as does furfuryl methacrylate,75 while rod-like molecules of
bis[4-(1,3-octadynyl)phenyl]terephthalate have been vapour deposited and then
UV cured.76 On the other hnad, monolithic macroporous polymers have been
prepared from functionalized methacrylate monomers.77 These monoliths were
prepared in spatially defined positions on fused slica capillary and microfluidic
chips. Deuterated MMA has been emulsion photopolymerized without an
initiator,78 whereas living amphiphilic poly(ethylene oxide) macromonomers
with varying p-vinylphenylheptyl end-groups have been made in micellar
media.79 High yields of a 1:1 alternating copolymer of styrene and MMA have
been prepared using BCI380 and dibenzyl trithiocarbonate81 as initiators.
Through both methods narrow polydispersed well-defined structures were
made. Allylic sulfide monomers have also copolymerized with MMA82 via a
pulsed laser system, while self-written waveguides have been prepared in a
photopolymerizable system,83 and 3D polymer structures made by Q-switched
laser irradiation of methacrylate monomers.84 Alternating copolymers have
been prepared from vinyl ethers and chlorotrifluoroethylene on account of their
marked differential polarities,85 while visible light has been found to photo-
polymerize MMA via azobisisobutyronitrile.86 Temporal variations in the homo-
polymerization of acrylamide have been monitored for holographic media,87 as
have molecular dynamics in glassy polymers.88 Polysilane-acrylamide copoly-
mers have been prepared for application on silica hybrid thin films,89 whereas
thin films of vapour phase poly((silyl)methyl methacrylate) polymers have been
grown continuously by irradiation.90 A benzilmonooxime methacrylate poly-
mer has been found to copolymerize and sensitize the photopolymerization of
MMA via benzyl and benzoyl radicals,91 poly[2-(10-unedecenoyloxy)ethyl
methacrylate] has been prepared92 and peptide functionalized amphiphiles have
been used to make liposomes.93
2.2 Photocrosslinking. – Various photoinitiator systems continue to be devel-

oped and investigated for photocuring and crosslinking or resins and polymer
materials. A series of novel oligomeric amine activators have been developed
for curing multifunctional acrylates,94 as have oligomeric benzoin ethers95,96
and acylphosphonates.97–99 With regard to the development of the latter, novel
acyl phosphine oxides have been bound to tetramethylene oxide side-chains
and their effectiveness as initiators found to be unaffected compred with free
initiator types.100 Similar conclusions were reached for novel camphorquinone
based polymeric initiators,101,102 while siloxane based photoinitiators have been
found to be less reactive.103 Novel vinyl-functionalized initiators have also been
developed with high efficiency,104 as have those based on cyclodextrin.105
Quaternary ammonium salts with aromatic ketone structures have been found
to exhibit photobase generating activities,106 whereas xanthene dyes have been
found to enhance the curing of acrylated resins via a benzophenone-amine
complex.107 Intermolecular transfer from the amine to the benzophenone is
enhanced by the dye, with sulfur based amines such as methionine being highly
Photochemistry, 36, 2007, 232–298 237
effective. Quaternary ammonium thiocyanates are also highly effective initia-

tors through photobase generation,108 as are zirconocenes.109 The latter were
found to be highly stable with an efficiency dependent upon the electron-donor
ability of the complexes and any steric effects.
Several cationic systems have also been developed. A number of commercial
systems include phenyl glycidyl ether,110 epoxy acrylates,111 prototype epoxies for
injection moulding,112 carbon fibre reinforced systems,113 diazonaphthoquinones
in Novolaks for deep UV curing,114 epoxy norbornenes for packaging applica-
tions115 and epoxy glass reinforced resins.116 Several accelerators have been
investigated for cationic curing. Benzyl alcohols have been found to be effective,
with efficiency being dependent upon the substitution pattern on the aromatic
ring.117 Here benzyl groups attach themselves to the ends of the polymer chains.
Pyridinium salts have been found to be accelerated by the addition of benzophe-
none,118 as have diarlyiodonium salts via iron-arene complexes.119 Macroinitia-
tors based on phenothiazine grafted vinyl ether groups are also highly effective
sensitizers120 especially for onium salts, as are telechelic polydimethylsiloxanes
modified with vinyl ether groups.121 Electron donating substiuents on the aro-
matic ring of trarylcyclopropenium tetrakis(pentafluorophenyl)gallates have been
found to slow down their activity by reducing their ability to release acid,122 whilst
the presence of N-vinylcarbazole is an accelerator for the iodonium salt induced
photocuring of glycol diglycidyl ether.123 Nitro substituted amines are effective
photobase generators in the curing of epoxide-thiol systems,124 whereas bis-
substituted diaryl iodonium hexafluorophosphate initiators work better through
a sensitization mechanism.125 Blends of poly(vinyl phenol)-diepoxides undergo
thermal cleavage processes,126 and the photocuring of butyl methacrylate in the
presence of dry triethylamine occurs through an anionic mechanism.127
The 2 þ 2 cycloaddition of polymer materials maintains some interest. The
photodimerization of styrylpyridinium groups bound to poly(vinyl alcohol) has
been found to be constant at 0.7 mol-% in solid films.128 The optimum degree of
polymerization for the chain was found to be 2500, with pH of the medium also
having an important influence on the rate of cure. Water soluble phenolic resins
with cinnamate groups have been prepared by a ring opening reaction of epoxy
phenolic and cinnamate groups.129 Similar polymers have also been prepared
based on polyesters.130 Polymers with p-phenylenediacryloyl moieties also un-
dergo a 2 þ 2 cycloaddition reaction.131 Temperature and solvent effects were
both found to be crucial. A new technique of solid-state crystalline photopo-
lymerization, called induction filming solid state photopolymerization, has been
developed, with the first polymer, crystalline poly(acrylamide), being developed
successfully.132
The photocrosslinking of polymer materials continues to be attractive in many
applications for electronic, electrical, insulation and property enhancements. N-
Isopropylacrylamide with di-methylmaleinimidoacrylamide has been crosslinked
to produce thermally sensitive nano-gels.133 These gels made in micellar media
exhibited major changes in hydrodynamic diameter in the vicinity of the phase
transition temperature of the polymer, with increasing temperature, micellar
concentration and chromophore content all decreasing particle size. Similar
238 Photochemistry, 36, 2007, 232–298
studies have been undertaken using di-methylmaleinimido-N-ethylacrylamide as

the chromophore.134 Here surface-plasmon resonance spectroscopy was used to
measure the degree of swelling and phase-transition temperature range of the
polymer. Film thickness reduced with increasing chromophore content. Various
vinyl benzene glycidyl ether based styreneic monomers have been cured via
azobisisobutyronitrile in the absence and presence of silane copolymers.135 In this
case, polymers with pendant 2-methylglycidyl structures were found to be more
reactive than those that were non-substituted, while an ether link between the
epoxy group and the aromatic ring lowered reactivity. Benzophenone induced
photocrosslinking of polyethylene has been discussed in detail,136 while a novel
di(4-hydroxybenzophenone)sebacate has been found to be effective for improved
compatibility in the same matrix.137 Phenylindene has been used as a crosslinking
agent for polystyrene via complexation with iron.138 Intramolecular crosslinking
was found to be the major process, with no oxidation of the iron complex owing
to protection by the polymer matrix. On the other hand, sodium benzoate has
been found to photocrosslink poly(vinyl alcohol) (PVA)139 through hydrogen-
atom abstraction from the polymer backbone followed by reaction with the OH
groups, giving rise to ether links between the chains. Similar photocrosslinking
studies were undertaken on PVA using furan and thiophene chromophores140
and PVC using sodium diethyldithiocarbamate as sensitizer.141 Fire retardant
polypropylene has been made by grafting with maleic anhydride and then
photocrosslinking with 2,3-dimethyl-2,3-diphenylbutane,142 and polyethylene
has been crosslinked via various quinones.143 Under 146 nm light, poly(vinyl-
phenol) has been silylated and coupled with crosslinking,144 while photosensitive
fluorescein polyurethane ionomers have been prepared145 and photocrosslinked
via benzoin. Novel polymer materials with 4-benzyloxy and 4-acryloyloxy func-
tionalities have been photocrosslinked,146 as have two-stage systems based on
benzaldehyde containing copolymers and quinones.147 Benzophenone has again
been used to photoinduce the crosslinking of acrylamide copolymers,148 and
acylphosphine oxides used to crosslink polybutadiene copolymers by doping
with multifunctional acrylates.149 The vulcanization of siloxane rubbers has been
undertaken via built-in oligodimethylsiloxane initiators,150 and hydrogels have
been made from N-cinnamoyloxymethyl acrylamide.151 Waxes have been found
to influence cure rates of wood finishes,152 and new prepolymers have been
developed from epoxy and methacrylic acid resin.153 Trapped radicals in the
photopolyerization of MMA polymers have been characterized via EPR154 as
well as their viability for 2D and 3D polymerizations.155 A new method for the
ultra prototyping of microfluidic systems using liquid-phase polymerizations has
been developed156 via plastic and glass cartridges. This process is shown to be
superior to that of conventional SU-8 50 photoresist technology. Phenylazide
end-capped copolymers photocrosslink effectively with increasing end group
concentration157 and are found to be effective for immobilizing cells. The
relationship between Tg and cure temperature has been monitored for a variety
of multifunctional acrylates.158 Here the differences were found to be signifi-
cantly greater for the more heterogeneous resins, thus facilitating a higher Tg as a
function of cure than is possible in a conventional homogeneous system.
Photochemistry, 36, 2007, 232–298 239
Polyamic acids are useful resists especially when containing 2,2 0 -dinitrodi-
phenylmethane segments,159 while a Ti:sapphire laser has been found to be
effective for 3D curing and microfabrication.160 On a theoretical note, a direct
correlation has been found between the calculated Boltzmann-averaged dipole
moment and the measured maximum rate of photoinitiated radical polymeriza-
tion of acrylic monomers.161
Liquid crystalline systems have important applications in optoelectronics. The
cholesteric structure of an ethylcyanoethyl cellulose/acrylic acid formulation is
somewhat changed upon photocuring.162 The wavelength for selective reflection
was shifted to higher energies coupled with a decrease in intensity, although the
variation ratio of cholesteric pitch after polymerization was not linear with
polymerization volume, the shrinkage ratio of the solvent and the polymer
concentration, though it varied with them. The discotic nematic phase has been
examined on a triphenylene based liquid crystalline material from the view point
of the effects of molecular orientation change due to polymerization.163 In this
case, there is a homeotropic alignment in the nematic phase when initially coated,
but following polymerization the order of the aromatic core in the nematic phase
markedly decreases during the early stages to a steady 80% of the total. When
using polarized light for curing, a series of methacrylate systems with substituted
biphenyl chromophores have been found to exhibit a small negative optical
anisotropy.164 Here 3D molecular reorientation and inclined out-of-plane re-
orientation was controlled by adjusting the exposure angle and nature of the
side-group. Similar functional monomers have also been developed165 where it
was found that the crosslinked polymer exhibited higher thermal stability that
that of the side-chain liquid crystalline material. The crosslinked material also
exhibited pyroelectric activity up to 1701C, whereas the side-chain polymers lost
their activity at 381C. Electrooptic and birefringence measurements showed that
crosslinking in the unwound smectic phase prevented the re-occurrence of the
helical superstructure. Highly ordered nanostructured lyotropic liquid crystalline
materials have been developed based on a cationic amphiphile.166 Both the type
and degree of phases formed depended upon the composition and temperature.
For example, the incorporation of a non-polymerizable surfactant gave hexag-
onal, bicontinuous cubic and lamellar morphologies. The last exhibited the
fastest polymerization rate due to diffusion restrictions associated with the highly
ordered state, with the slowest occurring in the less ordered hexagonal state. The
lyotropic liquid crystalline phase was, however, retained even above the thermal
phase transitions. For a group of 4-substituted acryloyloxy-cyanobiphenyl mon-
omers, orientation of the liquid crystalline textures was found to be retained on
photopolymerization.167 Only under isotropic phase conditions, were polygonal
or continuous phase-separated LC structures observed for dissimilar mesogenic
blends of monomers. A series of diglycidyl ether-bisphenol-A-aniline based
polymers have been prepared containing azo chromophores168 and found to
be useful for surface relief gratings, while the reflective wavelength range for LC
polymers can be modified by the chiral agent and temperature.169 Mono and
diacrylate dielectric networks have been prepared by in-situ photocuring of the
mesogenic reactive phase,170 as have switchable gratings from photopolyerized
240 Photochemistry, 36, 2007, 232–298
nematic diglycidyl ether diacrylate blends with polyether urethane acrylates.171

Fractal dimensional analysis has also been employed to obtain a quantitative
measure of the morphology of polymer networks produced by UV irradiation of
reactive mesogenic monomers in an LC host medium.172 Director gradient
controlled polymerizations have been found useful for assembling micron scale
polymer architectures,173 while a dichroic photoinitiator enables control over
polymerization kinetics through the state of polarization of the UV light used in
the initiation.174 In the latter case, when a chiral-nematic monomer mixture is
used in combination with polarized UV light, the polymerization kinetics are
modulated over the length scale of half the cholesteric pitch. This consequently
induces diffusion processes where the most reactive components of the mixture
will diffuse toward the volume area with the highest polymerization rate. Under
these conditions the helixes of the cholesteric networks formed were found to be
periodically deformed. When the deformed helix is combined with a pitch
gradient over the film thickness, the built-in retardation can be used for wide-
band cholesteric polarizers that directly generate linearly polarized light without
an additional quarter-wave foil. A photopolymerizable LC reactive mesogen
with high electron mobility has also been synthesized175 for CT media, and the
morphology of anisotropic networks formed in-situ in anisotropic solvents has
been extended to 3D by changing the polymerization direction during cure.176
Here the increasing homeotropic character of the anisotropic network resulted in
response times and threshold voltages that were lower than those of conventional
anisotropic gels.
Methods for monitoring properties of resins during photocuring continue to
attract interest. Pigmented177 and stabilized178 systems have been monitored, as
have acrylated systems through gellation and cure depth,179–181 EPR182 and
anti-solvent precipitation methods.183 Dilatometric184 and refractive index185
changes have also been measured. Differential scanning calorimetry is a com-
mercially viable method and able to differentiate rates and processes, although
volatile systems can be problematic.186,187 Real-time monitoring of infrared
changes in the curing of resins also continues to attract some interest. This
includes the use of the method for measuring temperature effects on photo-
curing,188,189 depth profiling190,191 and initiator concentration effects.192 Fluo-
rescence on the other hand is by far the most widely utilized technique,
although it must be said that the method is purely academic and is of little
or no interest to industry. Its use is primarily as a molecular probe to examine
the properties and nature of photocuring kinetics. In the photocuring of
acrylamide, the molecular probe, 1-anilinonaphthalene-8-sulfonate, has been
found to give enhanced fluorescence at the surface of the resin layers owing to
the hydrophobic nature of this region.193 Gel-phase transitions have also been
monitored in photocuring of MMA and glycol dimethacrylate,194,195 wherein
pyrene is used as the molecular probe. Here pyrene fluorescence lifetimes
decreased as swelling increased, no doubt owing to quenching and excimer
formation. In diglycidyl ether bisphenol-A196 and polyurethanes197 using
naphthalene and nitro-stilbene as fluorescence probes, changes in chemical
transformations, such as primary reactions of secondary amino groups, gel
Photochemistry, 36, 2007, 232–298 241
point and glassy state were all seen, with the method being developed further to
devise new mathematical models.198 The method is also viable for thermal
curing and has been demonstrated for phenolic resole resins.199 For acrylic
adhesives, double bond conversion rate was influenced by the actual molecular
size of the fluorescent probe,200 while dependence upon the microscopic envi-
ronment is also considered to be important.201 Fluorescent probes have also
been localized on the surface of epoxidized layers of resins using silane coupling
agents.202 Shifts in fluorescence emission maxima were related to depth and
degree of cure. The use of nitrostibene derivatives has also been shown to be
independent of temperature during cure203 as well as being useful for moni-
toring nanoscale mixing of formulations. Other curing processes exhibiting
success are cyclotrimerization of dicyanate esters,204 copolymerization of
bismaleimides205 and swelling in networks of polyethylene-poly(styrene-co-
butyl methacrylate).206 Using 7-nitro-2-oxa-1,3-diazol as a molecular probe,
fluorescence and DSC techniques have also been correlated.207
Reports of new materials and formulations and resin properties are prolific.
Articles of a topical or applied interest include probes for in-situ hardness
measurements on adhesives,208 photobase generators for image recording
devices,209 oxygen inhibition in packaging applications,210 resins for sign
boards,211 potentiometric sensors,212 new photodefinable polyimides,213 visible
curable resists,214 clay composites,215 putties,216 silica fillers,217 curable
paints,218,219 soluble photocurable systems,220 fluorinated coatings221 and in-
hibition processes on wood surfaces.222 In the last case, it is claimed that
phenolics from the wood surface inhibit the photocuring.
A number of hyperbranched systems have been prepared. These include
polyimides with methacryloyl groups at the chain ends,223 methacrylated
polyamine esters,224 polyurethanes acrylates,225 polyester acrylates226,227 and
polyisophthalate esters.228 All materials exhibit 3D sphere like structures with
excellent properties.
Sol-gel acrylated systems have been investigated and include organosi-
lanes,229 poly(L-lactide)-block-poly(ethylene oxide),230 bismethacrylates,231
methacryloxypropyltrimethoxysilanes,232 poly(N-isopropylacrylamide)233 and
N-cinnamic oxygenmethyl acrylamide.234 Apparently, in the Mir space station,
gel formation during photocuring is far more homogeneous than when carried
out on Earth conditions.235 Photosensitive polyimides are also high on the list
of useful materials. Novel interlayer dielectric polyimides have been prepared in
N-methyl-2-pyrrolidone solvent, giving values of 2.4–3.0 in the 1 to 20 GHz
region,236 while a series of polyamic acids have been made which were subse-
quently subjected to thermal imidization to polyimides237 for image generation.
The degree of photoreactivity of a series of polyimides has been found to
increase with constant UV exposure time238 owing to the presence of partially
crosslinked precursors. Polyimides with an indan structure have also been
produced239 with high thermal stability and transparency.
Polysiloxane based systems also have useful properties. Naturally occurring
phenols such as eugenol have been reacted with siloxanes to give excellent
photocrosslinkable systems,240 while polysiloxanes with oxaalkylene styrenyl
242 Photochemistry, 36, 2007, 232–298
groups form excellent release properties with good thermal resistance.241 The
photocrosslinking of vinyl polysiloxanes has been found to be more effective in
the presence of arlynitrenes compared to sulfonylnitrenes,242 whereas in an-
other study aromatic bisazides have been found to exhibit their highest value at
a 3% w/w concentration.243 Mesomorphic poly(di-n-alkylsiloxanes) have been
photocrosslinked in an iso-butyl acrylate matrix to give materials with prop-
erties varying from waxes through to plastics, depending upon the nature of the
alkyl substituent.244 The microscopic properties of these materials were found
by AFM to be dependent upon the degree of microseparation in the domains.
Phase separation has been measured in blends of (2,2-bis(4-(acryloxy diet-
hoxy)phenyl)propane and polysulfone.245 Bi-continuous phases were observed
at high cure temperatures while at low temperatures semi-interpenetrating
networks are formed. In epoxy modified acrylic copolymers, network hetero-
geneities were found to be strongly influenced by structure.246 An acid-resistant
water-based photosensitive MMA resin has been developed,247 as have diacry-
late resins with quaternary ammonium salts with excellent antistatic proper-
ties.248 Polyurethane acrylate adhesives have been found to exhibit excellent
optical and mechanical properties,249 while bifunctional sensitizers with both
initiation and grafting capabilities have been shown to exhibit high activity.250
Rather interestingly, humidity has been found to reduce the cationic photopo-
lymerization of epoxy resins.251 Polymers with endocyclic epoxy groups, how-
ever, show enhanced activity with humidity. Here there is a reaction between
the chain ends and water via proton transfer, and the more positive the end
groups the greater the degree of interaction. In the photoreaction of a series of
vinyl ether-oxirane based resins, induction times to curing are reduced by ethyl-
4-diethylaminobenzoate co-synergist,252 whereas a reaction between glycidyl
methacrylate and butane-1,4-diol in the presence of triethylamine gives glyc-
idol253 via a transesterification process. In terms of rates of cure, ITX has been
found to be the best of five intiators in phenolic resins containing quaternary
ammonium salts,254 concentration of photoinitiators in oligo(methacrylates)255
and polyurethane acrylates,256 methacryloyl content in polyether-poly-
urethanes,257 unsaturated methacrylic side groups in polyester-urethanes,258,259
free radical inhibitors in methacrylic-anhydrides,260 calixarene derivatives in a
variety of methacrylic and vinyl ether resins261 and calcium phosphate cements
in acrylamide polymers.262
High gel formation has been observed in the photocrosslinking of poly(eth-
ylene glycols), but only at the expense of high levels of benzophenone.263 On the
other hand, in the case of oligo(oxyethylene) with methacrylate groups, cross-
linking decreased with increasing LiCIO4 concentration,264 while the amount of
dissolution of the aggregated phase increased. Termination models have been
developed for the post-curing effects of a dimethacrylate monomer,265 whereas a
new oligomer based on the chalcone structure end-capped with methacrylic acid
has good thermal properties after cure.266 Light-sensitive naphthoquinone-(1,2)-
diazide-5-sulfonic acid esters have been developed as good positive photore-
sists267 with high solubility. A norbornyl epoxidized linseed oil has been devel-
oped and found to be poorer than that of an aliphatic epoxidized oil.268
Photochemistry, 36, 2007, 232–298 243
Triethylene glycol divinyl ether had to be added to give a good cure rate. Other
newly synthesized polymers include unsaturated polyesters with polyepoxy
groups,269 poly(3-methacryloylstyryl-2-naphthyl ketone),270 4-cinnamoyl-phenyl-
acrylate,271 digylcidyl ether diacrylate with polyurethane diacrylates for relief
plates272 and alkoxysilane methacrylates.273 Finally, the curing of 1,6-hexanediol
dimethacrylate has been investigated in a PMMA matrix,274 where interphase
attractive forces were important in controlling the film properties and the post-
cured photostability of commercial epoxy coatings has been studied.275
2.3 Photografting. – Surface modification continues to be utilized for property

modifications of materials. Nanostructred graft block copolymer micelles have
been developed,276 as have LC biphenyl monomers onto polyisoprene.277
Benzophenone has been used to initiate the grafting of acrylic acid onto
LDPE,278 as has benzoin for styrene onto polypropylene.279 In the latter case,
the surface was then sulfonated with chlorosulfonic acid followed by complex-
ation with metal ions, and utilized for ammonia adsorption. Polypropylene has
been light-stabilized through grafting of 2-hydroxy-4-(acryloyloxyethoxy)ben-
zophenone,280 and composite membranes of polyimides developed through
photografting of methyl acrylate via benzophenone.281 Novel particles with
designed hairs have been prepared by photografting acrylic acid onto core
particles of poly(N-isopropylacrylamide),282 while, from a scientific point-of-
view EPR, has confirmed cage effects in the grafting of acrylamide onto
poly(methacrylic acid).283 Blue leather surfaces have also been photografted
with dyed acrylated monomers,284 while styrene mono-layers have been grafted
onto gold surfaces.285 In reverse, polystyrene has been photografted with
2-hydroxyethyl methacrylate to give a material with an enhanced contact
angle.286 Membranes of polysulfones have been modified with different hydro-
philic monomers, such as N-vinyl-2-pyrrolidinone, to control protein permea-
bility.287 New LC materials have been made from an allyl(p-fluorocinnamate)
polysiloxane grafted copolymer288 with excellent thermal and alignment prop-
erties on ITO plates. Finally, the wettability of PTFE has also been modified
through photografting with N-isopropylacrylamide.289
3 Luminescence and Optical Properties
A number of reviews have appeared of topical interest. These include photo-

isomerization of azo dyes,290 photofunctional polysilanes,291 photochromic pig-
ments,292 rare earth complexes,293 pressure sensitive paints,294 electron-transfer
processes,295 electroactive dentrimers,296 chiral polyisocyanates,297 photodefin-
able benzocyclobutene,298 photoconductive polymers,299 excited states in conju-
gated polyenes,300 photosensitive materials301 and polyazomethanes.302
Urea linkages have been monitored during the extrusion production of a
polyurethane-urea through doping with a fluorescent aromatic diamine chain
extender,303 whereas soluble poly(arylene ether)s, thioethers and sulfones have
been synthesized, which emit strongly in blue and red regions.304 Brownian
244 Photochemistry, 36, 2007, 232–298
dynamics have been used to determine the distribution of fluorescent resonance

energy-transfer between the two ends of a stiff polymer chain.305 Collapsed or
ordered conformations were easily distinguishable by this technique. An ABA
triblock conjugated copolymer with strong two-dimensional quantum confine-
ment of excitons has also been synthesized,306 while on a more commercial
front 3-pyridinecarbonitrile compounds have been examined in paper formu-
lations,307 and fluorescent products have been removed from paper by thermal
treatment.308 Isothermal luminescence has been investigated from poly(ethyl-
eneterephthalate)309 and composite polyethylene.310 Luminescence from cross-
linked by-products311 and additives312 has also been monitored in polyethylene.
Luminescence has also been monitored in degraded isotactic polypropylene
tape,313 whereas diacetylene monomer has been polymerized into high molec-
ular weight polyethylene to produce a material with optical anisotropy for
security applications.314
Chemiluminescence of polymer materials maintains an active interest as an
analytical probe. The effectiveness of various commercial antioxidants in
polyethylene has been determined through their chemiluminescence activity
and related well to their ability to inhibit hydroperoxide formation.315 The
antioxidants themselves were also found to exhibit weak emission due to partial
oxidation of their structures during manufacture and storage. With tempera-
ture ramping, the chemiluminescence was significant and related well to the
melting points of the additives in the polymer. The same group of workers have
also shown that the chemiluminescence and activation energies for the thermal
decomposition of a series of polyolefins depended upon their rates of oxidation
under heat and light.316 On thermal oxidation the activation energies were
found to decrease with time and followed the order high density polyethylene
4 metallocene polyethylene 4 linear low density polyethylene, and this
correlated with the chemiluminescence. Similar results were obtained for
light-stability, with the overall effect being controlled by branching. Other
workers have indicated that the source of the chemiluminescence from poly-
olefins is a consequence of excitation energy remote from that of carbonylic
groups.317 Early prediction of the degradation of polymers is also possible by
this method318 as well as monitoring the photooxidation of cured resins.319,320
Localized chemiluminescence spreading in polypropylene has been confirmed
to be due to the generation of gaseous products such as aldehydes and acids,321
and charge couple devices have been useful for monitoring such effects.322,323
The kinetics of non-isothermal chemiluminescence of cellulose has also been
established as first-order,324 while the Fe catalysed decomposition of chitosan is
due to cleavage of the glycosidic bond via a six-membered intermediate giving
hydroperoxide radicals and a ketone group.325
Excimer properties in polymers have special interest in various contexts.
Polystyrene prepared by an anionic end-to-end coupling reaction has been
found to give anomalous emission between 300 and 320 nm, attributable to
styrenic chain end impurities.326 Other workers also associate polystyrene
emission with chemical defects in the main chain and optical impurity cen-
tres.327 In the same region (300–350 nm), excimer emission is observed, while
Photochemistry, 36, 2007, 232–298 245
longer wavelength emission is due to phenylhexatriene groups. Two different

time regions of excimer formation, on the other hand, were observed from
poly(methylphenylsiloxane).328 These were associated with a fast relaxation,
which is connected to unrestricted skeletal motions at the dyad level and a
slower relaxation, attributed to segemental chain rearrangements required to
release temporary isolated hindered monomer units; both being unaffected by
molecular weight. In the same polymer system, monomer fluorescence has been
associated with the diphenylsiloxane units, while the excimer emission does not
increase with Si–O content.329 The fluorescence of perylene-doped phenan-
threne in crystalline polymer media revealed the characteristic emission of
perylene and partial quenching of phenanthrene emission.330 Excimer forma-
tion due to perylene was not observed under these conditions, while in poly-
ethylene 1,3-di(1-pyrenyl)propane gives excimer emission which is temperature
dependent.331 In phenanthroline based polymers, the enforcement of a cisoid
geometry in the bipyridine unit of the main chain via an ethenylene bridge does
not significantly change the spectral and deactivation behaviour of the emission
processes.332 In the case of model systems, 2,2 0 -bipyridine analogues show an
intense bathochromically shifted emission due to excimer or aggregate states.
Poly(2,5-pyridinedyl), on the other hand, has been found to give blue fluores-
cence in solution and green emission in the solid state.333 The latter is associated
with phosphorescence, and delayed fluorescence is enhanced when associated
with oxygen. The electron-hole transporting properties of poly(aryl ethers) has
been enhanced through doping with carbazole and 1,3,4-oxadiazole mole-
cules.334 Dye-doping systems of this type have useful optoelectronic and
photonic applications.335 The photoelectric properties of N,N 0 -bis(4 0 -
aminophenyl)-1,4-quinonenediimine are influenced by the addition of a
heteropolyacid material,336 while rubrene doped in PMMA with N,N 0 -diphenyl-
N,N 0 -di(m-tolyl)benzidine appears to exist in two chemical environments.337 Some
novel benzofuranonaphthoquinol type clathrate hosts have been observed to
give rise to blue shifted emission on exposure to amine vapours,338 while, on the
other hand, the application of an external electric field reduces the emission
from thiacarbocyanine dyes doped in poly(N-epoxypropylcarbazole).339 Rotor
probes have also been developed for studying mobility in nanoscopically
confined polymers,340 whereas phenolphthalein doped into hydrotalcites can
act as useful probes for determing the physical properties of the material.341
Thus, the fluorescence of the dye gave emission spectra dependent upon
whether the dye was surface adsorbed or intercalated. Photogenerated triflic
acid in polyaniline has been used to alter its conductivity.342 Here delocaliza-
tion of electrons in the proton-doped polymer lowered the work function of
the polymer. Highly luminescent polymer zinc complexes have been prepared
from 8-hydroxyquinoline,343 while solvatochromic probes have been used to
measure solvent-water ternary mixtures where the emission of the probe
depends upon its partitioning.344 Polyimidazopyrrolone foils have been made
into 3D structures,345 as have optical sensors based on luminescence quenching
of platinum porphyrins.346 Protoporphyrins on the other hand have been used
to measure interpolymer adduct formation between self-organized mixtures of
246 Photochemistry, 36, 2007, 232–298
polycarboxlyic acids and poly(N-vinylpyrrolidone).347 Here the fluorescence

increases with degree of complexation due to the expulsion of water from the
phase. The kappa number of single fibres has also been measured using
Acridine Orange as a molecular probe,348 whereas the phototransformations
of naphthalene in cellulose have been shown to depend upon zone of loca-
tion.349 Fullerene dispersed in PMMA has been used as an optical molecular
thermometer,350 while the fluorescence from fullerene copolymers has been
shown to depend upon the aromaticity of the solvent.351 The ability of fullerene
to bind into a polymer is measured by the extent of quenching of doped
anthracene fluorescence.352 Fluorescence may also measure the extent of nit-
roxyl radical termination in polystyrene chains353,354 as well as the nature of
different polystyrene composites.355,356 The layer-by-layer deposition of poly-
styrenesulfonate and a water-soluble ionene permitted the formation of single
layer emitting devices.357 Real-time monitoring of fluorescence anisotropy has
been undertaken in biaxially stretched polypropylene film358 and has also been
used to measure the Tg of polymers.359 Fluorescent probes have been useful for
measuring polymer processing,360 water uptake in epoxy resins,361 polymeri-
zation of N-(1-pyrene)methacrylamide362 and micro-sphere formation.363
Fluorescence measurements on gels are numerous. These include gel forma-
tion and film thickness,364 photochemical switching365 and bilayer me-
mebranes366 in photocrossslinakble N-isopropylacrylamide, degradation in
kappa-carrageenan,367 molecular weight effects on PMMA gels,368 morphol-
ogy changes in styrene-divinyl benzene gels,369 self-assembly of gels based on
4,4 0 -bis(a-methylacryloyloxy-1,3-ethyeneoxycarbonylpropionamido)diphenyl-
methane,370 swelling in crosslinked PMMA,371,372 core-hair type microgels,373
photoreversibility in poly(ethyleneglycol) hydrogels374 and electroactivity in
acrylamide gel actuators.375
A highly polarized luminant polypyridine has been prepared through complex-
ation with camphorsulfonic acid followed by reaction with 4-hexylresorcinol,376
and for polyaniline the first hyperpolarizability and multiphoton induced fluo-
rescence has been observed.377 Polarized luminescence has also been reported
from poly(2,5-pyridinediyl)378 wherein side-groups may also be cleaved to give
solid films which retain their optical anisotropy. PMMA films have also been
prepared with a non-linear directional coupler379 where the coupler length
changes with the intensity of the light input. Poly(p-phenylene vinylene) (PPV)
has been modified through embedding it with wide-gap nanocrystals (antidots),380
thus altering the time distribution of the luminescence. The exposure of a
photosensitive poly(hydroxyaminoether)-based polymer to light leads to the
formation of an image with non-linear optical and photoelectric properties,
hence, photorefractive behaviour.381 A series of bifunctional acrylate monomers
have also been used to produce self-organized striped patterns of refractive
indexes.382 Using an electron probe, the striped patters were associated with
crosslinked density modulations in the cured resins. The photoluminescence
quantum yield of poly(9,9-dioctylfluorene) has been found to depend upon its
morphological state, with temperature, in turn, having an additional effect.383
Generally, temperature reduces the quantum yield as expected, except in the
Photochemistry, 36, 2007, 232–298 247
b-phase helix conformation, where a reduction in temperature reduces the quan-

tum yield owing to enhanced polaron formation, which can act as quenching sites
and traps for the singlet excitons. Production conditions for polystyrene com-
posites also affect their luminescence and optical clarity,384 while a copolymer
with terminal nitroxyl groups can be tagged with luminescent stilbene groups.385
The recording, relaxation and erasing cycles in a poly(malonic ester) with
p-cyanoazobenzene groups has been associated with reorientation of the polymer
backbone,386 while residual stresses in carbon black filled PVC doped with
9-methylanthracene may be monitored via surface fluorescence analysis.387 The
use of melamine formaldehyde particles has allowed the development of lumi-
nescent CdTe nanocrystal spheres,388 while a conductive polyaniline has been
prepared via doping and desposition with viologen.389 The optical properties of a
series of water soluble perylene tetracarboxylic diimide derivatives have been
determined.390
A number of articles have appeared on polyacetylenes and their derivatives.
Amplified spontaneous emission has been observed from poly(diphenylacety-
lenes) with Si and Ge substituents.391 The nature of this emission was found to be
dependent upon the nature of the substitution and the atoms. With the same
class of polyacetylenes, other workers show that electron-electron interactions
can cause enhanced delocalization of quasiparticles in the optically excited state
from the backbone polyene chain to the phenyl groups.392 On the other hand, in
urethane substituted polyacetylenes, irreversible thermochromic behaviour has
been observed.393 This type of conversion shows that there is a threshold of light
intensity which depends upon photon energy, indicating that the photoinduced
phase transitions in this polymer are mediated by the photogenerated electron-
hole pairs. Bis(biarylacetylenes) have been modified by oxidative cyclization to
produce effective narrow-band luminescent dibenzo(g,p)chrysenes,394 while po-
lyacetylenes with trans-4-n-alkylcyclohexanoate groups exhibit smectic LC be-
haviour, which apparently is enhanced on blending with PMMA.395
Photoluminescent silicate sticks containing nanodomains of conjugated poly-
mers segregated by ordered silicate channels have been prepared from diacety-
lene surfactants.396 The sol-gel route for these materials produced excellent
nanostructured optoelectronic and electroconductive materials. Carbazole side
groups in polydiacetylenes have been found to be responsible for a peculiar
supramolecular organization seen in the powdered phase of the red form of the
material,397 while the fluorescence of mono-layers of polydiacetylenes has been
measured and compared with those from single crystals.398
There are a number of studies on pyrene labelled or doped polymer mate-
rials. Dendritic size and electrostatic forces in poly(amido) dendrimers with
pyrene residues have been determined through the use of a variety of quenc-
hers.399 As the dendritic size increases so the Stern-Volmer quenching constant
decreases, owing to blocking of the pyrene chromophore by the growing
dendritic network. The photophysical properties of poly(acrylic acids) tagged
with pyrene has been measured in micellar media at various pHs.400 The ratio
of monomer to excimer gave valuable information on the micropolarity sensed
by the pyrene label, as well as the influence of external stimuli. The surfactant
248 Photochemistry, 36, 2007, 232–298
was found to interact with the polymer at a pH 3 to form a complex with a

critical aggregation constant lower than that of the CMC of the surfactant.
Similar studies have been undertaken on poly(sulfone-amine) labelled with
pyrene401 where the excimer emission increased with increasing hydrophobicity
of chain branches. The hydrophobicity of nanodomains in heat-induced pre-
cipitation of poly(N-isopropylacrylamide) has also been monitored through the
excimer emission of pyrene tags.402 Poly(N-propargylamide) tagged with pyre-
ne has also been shown to respond rapidly to changes in temperature,403 while
chiral interactions in poly(N-1-(1-pyrenyl)ethyl-1-glutamines have been found
to affect excimer formation.404 Aggregation and precipitation effects have been
determined for pyrene tagged polystyrene in solvent-water mixtures,405 and
thermal relaxations monitored in pyrene probed nylon406 and EVA407 poly-
mers. In the last case, no simple relationship was found between the relaxation
processes and the vinyl acetate content, which could be explained by the
morphology of the copolymers. In a similar way pyrene probed PMMA has
measured the extent of desorption of polymer chains from disks.408 Pyrene has
also been shown to exhibit negative desorption from crosslinked polystyrene
nanoparticles.409 The interesting feature in this work was the observed marked
40-fold enhancement in the pyrene emission compared with solution media.
Self-assembly of hydrous metal oxide states has also been monitored for
zirconia media using 1-pyrenecarboxylic acid as a probe.410 Radical-ion re-
combination processes in pyrene doped PMMA have also been monitored,411
as have phase changes in hydrogen-bonded gels of poly(methacrylic acid-co-
dimethyl acrylamide).412
Light emitting diode polymers (LEDs) are the subject of the most prolific
area in this field at this point in time, followed closely by photochromic
materials. Triple bonds have been incorporated into the PPV backbone to give
excellent electron transporting materials413 for LEDs. Although the basic
unsubstituted polymer had a high fluorescence quantum yield, significant
reductions were observed on alkylation to give more processable materials.
In another study, electron attracting, octafluoro biphenyl and hole transport-
ing, carbazole and dialkoxyphenyl groups have been incorporated into PPVs
wherein conjugation length had restricted the emission to the blue region giving
poor device performance.414 Rod-coil block copolymers of PPV have been
made with styrene and ethyl acrylate,415 while other workers have prepared a
whole range of PPVs and categorized them in terms of LED efficiency.416 A red
coloured PPV with C1–4 chains has been prepared, but is restricted by solvent
solubility,417 as are PPVs treated with N-chlorosuccinimide.418 Model
compounds of PPVs have been examined in micellar media,419 and novel
solvent- and water-soluble materials have also been prepared.420,421 Poly(thiop-
hene-phenylenevinylene) has been characterized to give efficient intramolecular
energy-transfer and self-assembly ability,422 while biphenyl and terphenylene
derivative of PPV have high thermal stability.423 Two main electron traps have
been identified in poly[2-methoxy-5-(2 0 -ethylhexyloxy)-1,4-phenylene vinylene]
wherein the activation energies and level filling was enhanced by exposure to
air.424 The deeper traps were located near the surface, in the contact region,
Photochemistry, 36, 2007, 232–298 249
while the shallower traps were located across the depth of the material. In this
material, the re-application of a charge was found to give rise to long-lived
polarization due to some possible chain restructuring. In fact, electron-hole
capture processes in PPVs have been modelled by the dissipative dynamics of a
multi-level electronic system coupled to a phonon bath.425 In this model, the
authors have considered the recombination kinetics of an initially separated CT
pair and address the issue of electroluminescent enhancement in LEDs. Overall,
a remarkable linear relationship has been found between chain length and
singlet-triplet branching ratio, which was explained in terms of the binding
energies of the final excitonic states. PPVs with 1-4 styryl units have also been
characterized in terms of their vibronic coupling.426
PPVs with various alkoxy groups have been prepared and characterized.427
Thermotropic and lyotropic behaviour was observed, coupled with a high
degree of electron affinity and good photoconductivity. Although the nature of
the substituent affects the emission maxima and quantum yields, the octyloxy
group gave the highest yield, with narrow spectral emissions. Long chain
hydrocarbons induced high solvent solubility and intense red colouration,
but strong interchain interactions caused significant quenching and excimer
formation. PPVs with p-terphenyl groups in the main chain give violet-blue
emissions due to well-defined chromophoric interactions,428 while PPVs with a
different trans-olefin configuration give green emissions.429 Shifts in emission
maxima and concentration effects have also been undertaken on the octyloxy
PPV,430,431 while a new dibromo PPV gives green emission at 492 nm with a
very high yield of 72%.432 Thermally stimulated emission from PPV has been
found to contain two peaks, an upper due to intrinsic localized states and a
lower one due to aggregates.433
Carbazole containing PPVs are high on the list as effective LEDs. A number of
similar studies relate to the formation of novel systems with carbazole groups
with high solvent solubility and greenish-blue photoluminescence with high
efficiency.434–437 The incorporation of carbazole groups with octyl groups give
good solubility and spin coatability, displaying two reversible redox processes,438
while the incorporation of PVK directly into PPV gave a 2.5-fold enhancement in
emission intensity.439 PPVs with pendant carbazole groups give green emissions,
the lower wavelengths providing more effective LEDs.440
Doping or reacting with metal complexes or salts is also proving attractive for
LED devices. Vinylene linked PPVs doped with antimony pentachloride have
been found to give new red-shifted optical absorption bands due to CT spe-
cies,441 whereas those doped with poly(pyridinium salts) exhibited thermotropic
LC properties.442 New azo-conjugated ferrocene oligomers have been shown to
give unique redox behaviour443 as well as green light isomerism due to strong
electrostatic interactions. Other PPVs with thienylenethynylene groups show
sensitivity to doping with transition metal ions,444 whereas PPVs substituted with
crown ethers exhibit worm like images when complexed with potassium ions.445
These images apparently grow slowly on account of self assembly and complex-
ation with the K1 ions. The photosensitivity of PPVs has been shown to be
enhanced upon doping with Ru and Rh diimine complexes.446 Here the CT
250 Photochemistry, 36, 2007, 232–298
process is facilitated beyond 500 nm, with carrier mobility being dependent upon
the metal content in the polymer. Other studies include coating PPVs onto gold
substrates447 and reaction with iridium derivatives.448
PPVs based on triphenylamine have been studied. Pure poly(triphenyla-
mines) have been made and found to exhibit high blue emission quantum
efficiencies of 0.78,449 while PPVs with triphenylamine in-chain functionality
have good hole-injection ability and high mobility450–452 and strong yellow
emissions. PPVs with 1,2-diphenylmaleimide groups in the backbone, on the
other hand, exhibited a curing process in the temperature range 165–2501C
owing to crosslinking between acetylenic groups.453 These polymers also give
yellowish-green emissions.
Fullerene containing systems are also of interest and have been covered in
some detail in terms of applications and properties.454 Strong photoenergy
transfer has been observed between pendant fullerene groups in PPV copoly-
mers and main chain chromophores, especially at low temperatures.455 In PPV-
fullerene composite films, an increase in the substituted side-chain length has
been found to lower the energy of the emission bands, while the fullerene
dopant also quenched the emissions. In this way the electronic affinity of the
PPVs can be controlled.456 Conjugated polyelectrolytes also have applications
as fluorescent sensors.457
Several types of siloxane based PPVs have also been developed with good
processability and LED efficiency. Highly soluble cyclohexylsilyl and phenyl-
silyl PPVs have been prepared with high molecular weight and electrolumines-
cence performance (0.82) with emission maxima at around 512 nm.458
Poly[(formylphenyl)methylsilanediyl] has also been prepared and tagged with
pyrene and biphenyl molecules, to give highly electroluminescent materials in
double layers of up to 0.06%.459 Ladder-like poly(phenylsilsesquioxane) has
been prepared and found from excimer-monomer emission ratios to give a
linear Arrhenius plot with one break point, typical for polyorganosiloxanes.460
Thermotropic LC behaviour has been observed in poly[2,5-bis(dime-
thyloctylsilyl)-1,4-phenylenevinylene], coupled with a high LED output in
multilayer systems.461 Oligophenylenevinylenes have also been directly
attached to a Si atom to give blue-green emitting products,462 while other blue
emitting products include poly(2,5-dialkoxy-1,4-phenylene/1,3-divinyl-1,1,3,3-
tetramethyldisiloxane)s,463 polymers coupled to 2-trialkylsilyloxy-6-methylphe-
nol464 and various oligocarbosilanes.465
Fluorene containing polymers exhibit interesting LED properties. These are
based on poly[9,9-bis(20 -ethylhexyl)fluorine-2,7-diyl-co-2,5-bis(2-thienyl-1-cyano-
vinyl)-1(2 0 -ethylhexyloxy)-4-methoxybenzene-500 ,5000 -diyl] with strong absorption at
380 nm, increasing with thiophene addition,466 poly(quinoxaline-fluorene) with
blue emission at 447 nm and absorption at 407 nm,467 polyfluorene derivatives
with emission at 420 nm,468 highly soluble poly(9,9-di-n-hexyl-2,7-fluorene-diyl-
ethynylene-alt-9-trimethylsilyl-2,7-fluorene-ethynylene) with emission maxima at
490 and 540 nm,469 blue emitting copolymers of fluorene and oxadiazole,470 green
emitting polymers based on 9,9-dialkyl-fluorene-2,7-diboronate esters.471 A red
emitting copolymer at 675 nm has also been made based on diocylfluorene and
Photochemistry, 36, 2007, 232–298 251
4,7-dithien-2-yl-2,1,3-benzothiadiazole472 and blue light emitting poly(2,7-fluor-

ene) networks.473 A hypsochromic shift of the new fluorescence spectra in PPV
doped trinitrofluorenone has been interpreted in terms of increasingly frustrated
spectral relaxation of singlet excitons within a homogeneously broadened distri-
bution of hopping states.474
PPVs with oxadiazole groups are also useful LEDs. Two new luminescent
copolyethers with isolated 2,5-distyrylthiophene emitting groups and electron
transporting 2,5-diphenyl-1,3,4-oxadiazole chromophores have been pre-
pared.475,476 These highly soluble materials have good LED characteristics
with yellow-green light. PPVs with oxadiazole chromophores also give green
emission with excellent LED properties as a triple layer device.477,478 Highly
thermally stable poly(oxadiazole-amides) with good solvent solubility give blue
emission and form excellent devices on Si wafer on the nanoscale.479 Poly(p-
phenylenebenzobisthiazole) is a rod-like polymer with similar properties and is
voltage tunable.480
A benzothiophene PPV copolymer has been found to be photochromic,
turning bright red upon irradiation owing to the formation of a ring closed
dimer481 with a high quantum yield and, as such, could have considerable
potential in optical reading systems. Thienyl building blocks in PPVs also
enabled photoluminescence tuning,482,483 while those bearing coumarin,484 N-
alkylcarbazole,485 iodine,486 imides,487 paracyclophane,488,489 anthracene490,491
and dinaphthylanthracene492 give blue emissions with good LED properties.
Soluble and thermally stable diyne containing PPVs have been synthesized.493
Here the energetically arduous migration of electrons through the diyne units
required a higher threshold voltage for the detection of photoconduction,
although the electron withdrawing effect of the triple bonds conferred good
electron accepting properties suitable for LEDs. Chemiluminescence has also
been generated from PPVs electrochemically, with anodic polarization giving a
higher efficiency.494 A series of arylamine crosslinked polymers have been tuned
for LEDs,495 while LC polyfluorenes have been successfully aligned on photo-
addressable polymers such as polyacrylates with mesogen azobenzene side
groups.496 Patterning with laterally structured alignment was realized in several
ways, utilizing reorientation with orthogonally polarized light. Conductivity in
poly(1-hexyl-3,4-dimethyl-2,5-pyrrolylene) has been correlated to chain struc-
ture and conformation as well as the torsion angle of the pyrrole bonds,497
whereas nanocrystal formation in pyridine-doped poly(4-vinylpyridine) is un-
dertaken by ring-opening followed by photoproduct aggregation.498 PPVs have
been made with ionically conductive triethylene oxide units that are soluble and
excellent LEDs,499–501 while several blue-orange polythienylenes have been
made with LC properties giving while luminescence.502 Biphenyl poly(1-al-
kynes) have been found to developed enantiotropic SmA and SmB mesophases
when the spacer length was increased to 4.503 LED properties are also enhanced
in a similar fashion. A new fluorescent instrument has also been made using an
array of LEDs,504 while poly(vinyl toluene) becomes luminescent upon irradi-
ating with ionizing radiation.505 LED devices have been made from norbornene
and Al 8-hydroxyquinoline,506 polyamic acids with quaternary ammonium
252 Photochemistry, 36, 2007, 232–298
salts,507 polyphenylene dendrimers,508 2,6-linked quinquepyridine deriva-

tives,509 polyquinolines,510 polypyridinium salts,511 tritolylamine in polycar-
bonate,512 PPVs with aldehydic and aminooxy groups513 and carbon
nanotubes.514 PPVs with pyrazine groups gave suitable red-shifted emis-
sions,515 and in pyridine based PPVs the chain rigidity could be controlled.516
Femtosecond spectroscopy has been used to measure electronic excitation
oscillations in PPVs,517 whereas electric field induced fluorescence quenching
and optical charge generation in poly(p-phenylenes) is associated with exciton
dissociation into geminate electron-hole pairs rather than their full dissociation
into free charge carriers.518 Delayed fluorescence in the same polymers has been
associated with the same process,519 whereas intersystem crossing rates have
been found to be the highest in polythiophenes.520 PPVs with fluorine groups
showed a stable enantiotropic Sc phase, characteristic of ferroelectricity as well
as fluorescence,521 while the geometries of PPVs and their ramifications have
been optimized by using a quantum chemical method.522 Time-dependent
excitation studies on PPVs shows that self-trapping of excitations occurs on
about 6 repeat units during the course of photoexcitation relaxation, as well as
specific slow torsion and fast bond-stretching nuclear motions, all strongly
coupled to the electronic degrees of freedom.523 At low temperatures PPVs
occupy a more planar structure,524 whereas the photostability of PPVs can be
enhanced by doping into silica nanoparticles,525 silicate composites526 and
treatment with solvents like THF.527
The optical properties of polythiophenes have been actively investigated. A
series of 3,4-disubstituted poly(thiophenes) have been made, with the nitro
derivative exhibiting a large Stokes shift of 218 nm associated with the planar
geometry of the group lowering the excited state energy level.528 Phenyl substi-
tuted polythiophenes exhibit two well defined ordered-disordered phases,529 the
conductivity being enhanced via the addition of fullerenes. The blue phase has an
enhanced spectral absorption range, with strong bimolecular recombination when
compared to that for the orange phase, which is more appropriate for LEDs.
Regular bithiophene-alt-thiophene-S,S-dioxides have been made by aniodic cou-
pling and exhibit a finite window of conductivity.530,531 Here the dioxide substi-
tution tends to increase the torsion angle between the rings, thus influencing the
states at the optical band edges. Polythiophenes with pendant fulleropyrrolidine
moieties operate as double cable polymers for LED applications,532,533 while
other workers534 have shown that the LED properties of polythiophenes decrease
upon continuous irradiation owing to the growth in photooxidation products.
Both phosphorescence and delayed fluorescence have been observed from poly(3-
methyl-4-octyl-thiophene)535 owing to geminate pair decay, while the potential of
such materials for LED applications have been determined through a structural
versus efficiency evaluation.536 Carbazole groups, on the other hand, have been
shown to reduce the photoluminescence efficiency of polythiophenes,537 whereas
in blends of poly(vinyl alcohol) with poly(3-thiopheneacetic acid) emission in-
tensities are enhanced through laser irradiation.538 Rigid cyclic polythiophenes are
also highly emissive,539 as are m-linked polythiophenes.540 A new poly(3-phenyl-
galvinoxylthiophene) has been made and shown to undergo a reversible blue-red
Photochemistry, 36, 2007, 232–298 253
colour change due to radical and anion formation,541 whereas poly(2-et-

hynylthiophene) undergoes cis-trans isomerization.542 Other systems of interest
include conformational changes in poly{3-[2-(N-dodecylcarbamoyloxy)ethyl]-
thiophene},543 poly(arylene ethynylenes) doped with polythiophenes,544 crystalline
oligothiophenes,545 ring closure in a dithiophene containing polymer,546 nano-
molecules from oligo(octithienylene-diethynylenes)547 and chiral assemblies of
amphiphilic polythiophenes in aqueous media.548
Electron- and energy-migration processes cut across numerous systems.
Triplet-triplet annihilation due to intra-chain diffusion exhibits bimolecular
reaction kinetics associated with a turnover from dispersive to non-dispersive
regimes, as borne out by the delayed fluorescence decay.549 Millisecond pho-
toexcitations in poly(p-phenylene sulfoxide) are due to triplet excitons and not
ring-torsional polarons found in previous polyanilines.550 Intersystem crossing
processes have been manipulated in 4-thienyl polymer systems,551 and a new
series of donor-acceptor trivalent boron systems developed with two-photon
excited up-conversion fluorescence.552 An analytical expression has been de-
veloped to account for luminescence from a polymer chain in the static regions
where rotational motion of monomers giving excimer formation is frozen.553
The conditions are apparently found when the inhomogeneous broadening of
the chromophoric spectra and conformational motion of the polymer chain
should be taken into account. A mathematical model has also been presented to
show that the up-gap state of a polaron possesses negative polarizability,554
whereas, for polymers with randomly labelled chromophores, analytical equa-
tions have been obtained for donor-decay curves for both pseudo-ideal and
self-avoiding walk polymer chain models.555 Photocarrier transfer theory in a
photorefractive polymer has also been developed556 to give analytical solutions
and numerical data for both temporal and steady-state processes of space-
charge fields in materials under different conditions. The results of a Brownian
dynamics simulation of the time-dependent survival probability of a donor-
acceptor pair embedded at the two ends of a Rouse chain have been compared
with the well-known Wilemski-Fixman (WF) theory.557 While the WF theory
has been found to be satisfactory for small reaction rates, the agreement was
found to be progressively poorer as the rate was increased. In this theory an
approximate reduced propagator technique was introduced for a 3D system
and then solved by combining a Green’s function solution with a discretized
sink method. Poly(Schiff’s bases), in which non-radiational energy transfer
occurs, have been made,558 whereas trifluoromethyl-norbornadiene donor-
acceptor moieties exhibit repeated cycles of interconversion.559 Intramolecular
energy transfer has been confirmed via femto-second laser photolysis experi-
ments,560 as has photoinduced electron-transfer acid generation due to intra-
molecular conjugated CT in triazine compounds.561 Only triplet excitons have
been observed in alkyl methacrylate polymers with halogenated carbazolyl
pendant groups,562 while CT processes have been observed in poly(acrylonit-
rile)-C60 copolymers.563 Ultrafast electron-transfer reactions have been initi-
ated by excited CT states of push-pull perylene systems,564 whereas in CT
complexes of copolymers of naphthyl methacrylate with vinyl carbazole exhibit
254 Photochemistry, 36, 2007, 232–298
only naphthalene fluorescence at low concentrations.565 Conjugated polymers

with longer excited state lifetimes than those of phenyl analogs have been
designed based on triphenylene poly(arylene ethynylenes),566 while electron
transporting copolymers have been developed containing 1,3,4-oxadiazole
groups.567 Polyfunctional carbazole containg methacrylate copolymers also
exhibit highly efficient energy migration,568 as do novel discotic triphenylenes
with a comblike polymethacrylate wrapping.569
Dendrimers continue to display interesting photooptical properties. Charge
transfer and applications of dendrimers have been well covered.570–573 Poly-
arylether dendrimers have been found to be highly effective at shielding
phosphorescent Pd porphyrins from oxygen,574 while the analysis of dendrim-
er-embedded polymers indicated that, upon hole burning, the structural relax-
ation of polymer chains outside the dendrimer does not have an influence on
the resonant frequency of the porphyrin core.575 Hyperbranched PPVs exhibit
significant red-shifted emissions,572 whereas poly(3,4,5-trihydroxybenzoate)
dendrimers give strong chemiluminescence.576 Exclusive Forster energy trans-
fer is observed from dendrimers with four donors and one acceptor chromoph-
ore.577 Donor emission is observed only following bleaching of the acceptor
molecule, which in this case is terrylenediimide. A perylene diimide dye has
been used to build-up a polyphenylene dendrimer to give a pentaphenyl
building block.578 In this case, however, although aggregation is prevented,
the fluorescence quantum yield decreases with increasing generation. Dend-
rimers with all-azobenzene repeat units have been prepared for the first time,579
as have photochromic dendrimers with six azo functionalities.580 In poly(pro-
pylene amine) dendrimers with naphthalene and trans-azobenzene units, elec-
tron transfer from the amine groups quenches the naphthalene fluorescence.581
In this process, the trans-azobenzene units are converted to the cis form.
Phosphorus dendrimers with azobenzene groups have also been made wherein
isomerization from the E to the Z form is the primary reaction on irradia-
tion,582 with little change in reaction rate versus generation number. Azoben-
zene groups deep in the framework, however, showed different kinetics. The
kinetics of hyperbranched polystyrenes have been investigated via a photo-
functional thio inimer583 and perylene initiator.584 In the latter, the polystyrene
arms were found to suppress aggregation of the perylene chromophores and, at
low degrees of polymerization, the rigid-core moiety significantly affected the
segmental motion of the arms. Spin casting gave films with a high fluorescence
quantum yield and additional properties for migration fastness. Self-associa-
tion has been observed in hyperbranched poly(sulfone-amines)585 where the
excimer emission from a perylene probe was found to give an intersection at
35%. Phenyleneacetylene dendrimers have also been labelled with perylene,
with potential applications for fluorescence based thermometry.586,587
Poly(propyleneimine) dendrimers, on the other hand, functionalized with
oligo(p-phenylenevinylene) end-groups based on distyrylbenzene show fluores-
cence which is dependent upon the generation number.588 Rapid migration of
exciton energy and chain coupling caused a red-shift in the emission spectrum,
implying that interchain interactions are very strong, causing delocalization
Photochemistry, 36, 2007, 232–298 255
over more than one group. Delayed emission was also observed from the
dendrimer but not the isolated units. Highly luminescent distyrylstilbenes
bearing oxadiazole surface functionalized poly(benzyl ether) type dendritic
wedges at one end have been prepared.589 This novel system shows for the fist
time that an emissive core bearing asymmetric substituted functionalized
dendrons exhibits more favourable luminescence than that of a symmetrical
core. Energy-transfer efficiency was found to be extremely high with excellent
LED properties. A six-generation methyl orange functionalized poly(propyl-
eneamine) dendrimer has been made with both pH and light sensitivity.590 The
isomerization process showed no dependence upon generation, while pH did.
In a similar fashion, phenol blue has been bound to poly(propyleneimine)
dendrimers.591 In solution two discrete dye populations were observed in the
inner and outer cores. Carboxylic diads have also been bound onto the same
dendritic structure,592 where in this case intermolecular ionic interactions were
observed to form templates. A quinoline tautomer bound to a poly(aryl ether)
dendrimer has been found to influence and decouple the excited state intra-
molecular proton-transfer process as well as the core planarity.593 Although the
rate was found to be slowed with increasing generation number, the lumines-
cence still increased owing to the formation of isolated surface units. Dend-
rimers based on 5-aminovulvinic acid have been used for photodynamic
therapy,594 while chiral dendrimers have been made based on bi-2-naphthyl
cores.595 Photocrosslinkable dendrimers have also been made based on
poly(1,5-dioxepan-2-one).596
Various tagged polymer systems have been investigated as optical probes.
Fluorene based and oxadiazole substituted polymers have been made597,598 in
order to facilitate electron-migration processes, as have poly(aryl ethers) with
carbazole and fluorine groups599 and poly(methyl acrylate) grafted with
poly(thiophene).600 In the solid state, the acrylate traps the thiophene polymer
into a solution-like state. For dansyl sulfonate tagged groups to an E-type
glass, it has been found that the solvent dipolar coupling relaxation mechanism
is dominated by thermodynamic interactions of the polymer with the solvent in
aprotic media, while in protic media this mechanism is dominated by specific
interactions between the solvent molecules and the excited state chromoph-
ores.601 Poly(styrene-co-maleic anhydride) has been tagged with a 1,8-naph-
thalimide dye602 and aminobenzothiazoles603 to give fluorescent sensitive
systems, as have cationic poly(acrylamides) with various anthracene, pyrene
and dansyl groups604 as quantitative probes. Using acenaphthalene as a probe,
poly(vinyl pyrrolidone) has been shown to adopt a loose coiled conformation
over a wide pH range.605 This polymer unusually binds to molecules with active
hydrogens and can be used, therefore, to modify the conformational behaviour
of some water-soluble polymers with hydrophobic micro-structures. The fluo-
rescence properties of Schiff’s bases are also affected by the cationic or anionic
form of the amine groups,606 and the fluorescence of 2,2 0 :6 0 ,600 -terpyridines is
significantly influenced by the solvent and the number of pyridine rings.607 The
question of intermixing of hydrocarbon systems has been investigated through
the use of pyrene labelled poly(N-isopropylacrylamides).608 In micellar media
256 Photochemistry, 36, 2007, 232–298
excimer formation indicated that polymeric chains can exchange among mice-
lles of hydrocarbon-modified polymers, but not hydrocarbon and fluorocarbon
modified polymers. The latter were found to segregate into nanodomains
within a hydrophobic core. The same study and polymer system has been used
to measure the mixing of hexane and methanol, where the rotational motion of
chromophoric groups is slowed down at the critical mixing point.609 Molecular
orientation has been investigated through the use of polyethers with quinque-
phenyl and anthracene segments.610 Using CD measurements, the polymer
chains have been found to orientate parallel to the direction of the draw, giving
polarized blue and yellow light emissions. Superquenching has been observed
on silica spheres containing cyanine dye bound polylysine,611 cogelation mon-
itored in trimethoxysilane-derived oligarylene-vinylene fluorophores,612 ther-
mal properties of PPMA copolymers with benzazolylvinylene chromophores
determined,613 tunable electrochemical interactions observed in polystyrenes
with anthracenyl and tetrathiafulvalenyl groups,614 crosslinking achieved in
fluorene containing polymers615, energy transfer examined in N-allyl-2-amino-
benzoic acid and benzamides,616 processing effects on pyrene tagged acrylate
and vinyl pyridine polymers studied617 and polymerizations with 9-acrydyl
derivatives of aromatic amines monitored.618 Fluoroalkyl end-capped cool-
igomers containing benzoylbenzyl segments have been found to have excellent
oil repellency on polymer surfaces such as PMMA619 as well as antibacterial
and anti-HIV activity in-vitro. Water-soluble conjugated ionic poly(et-
hynylpyridinium bromide) exhibited good film properties,620 oxypyridinium
functionalized methacrylates and styrene undergo intramolecular cyclization
reactions,621 cyanine dyes in PMA undergo photoisomerization,622 and 1,8-
naphthalimide dyes have been bound to styrene.623
The optical properties of polymers in micellar media are widespread in
interest. Only the protonated base of Acridine Orange dimerizes in water-
heptane media.624 At pH 4 10 only the basic form is detected in heptane, while
at a pH 4 above the critical micelle concentration the basic form disappears
giving the protonated dimer. Overall, three processes were identified: (1) the
distribution of the dye between the organic phase and the micellar interface
followed by protonation to give the mono form, (2) dimerization of the dye at
the interface and (3) the conversion of the dimer form to the mono form by the
micelle at high dye concentrations. The important parameters that are respon-
sible for the solid-matrix phosphorescence quenching of phosphors adsorbed
onto filter paper have been determined for phenanthrene and benzo[e]pyre-
ne.625 Here the changes in phosphorescence intensities and lifetimes followed a
simple exponential function with moisture content and were due to changes in
the modulus of the paper. Ultrasonic methods have also been used and
compared with fluorescence analysis to determine critical micelle concentra-
tions of liposomes and surfactants.626 Here the CMCs were found to increase
dramatically with an increase in the polymer chain length. Amphiphilic comb-
shaped polymers based on a hydrophobic poly(p-alkylstyrene) with a hydro-
philic poly(ethylene oxide) graft have been examined in water using a pyrene
probe.627 Direct observation of a single macromolecule revealed a high
Photochemistry, 36, 2007, 232–298 257
molecular weight cylindrical brush-like conformation of 12.8 nm thickness.

Fine particles were also observed, suggesting the formation of a unimolecular
micelle in water. In polyelectrolyte samples of poly((2-acrylamido)-2-methyl-
propanesulfonic acid)), energy transfer between pyrene and naphthalene probes
showed that the charged polymer chains interpenetrated each other rather than
reduce their coil volume.628 By binding with surfactant, the polyelectrolyte
chain became more coiled, with intramolecular energy transfer occurring below
4 105 M and intermolecular energy transfer occurring above it, eventually
giving hydrophobic aggregation between the micellar tails bound on the
polyelectrolyte chains. On the other hand, polyion complex formation between
polylysine and chondroitin sulfate has been measured in the presence of
pararosaniline leucohydroxide.629 Between pH 6 and 12, the chondroitin was
fully dissociated, while the polylysine is reduced with increasing pH, resulting in
a random coil-to-a-helix transition around a pH 9.4. Complex formation was in
fact controlled by irradiation. The aggregation behaviour of a biodegradable
amphiphilic poly(aspartic acid) with long alkyl chains has been characterized
by size, interfacial properties and aggregate formation.630 These polymers
formed aggregates on ultrasonication, with higher amounts of alkyl chain
grafts inducing higher aqueous stability of the self-aggregates. In aqueous
media the incorporation of a C18 chain did not produce surface activity owing
to the physical crosslinking nature of the octadecyl chains. Shorter chains were
surface active. Aggregated assemblies of hexadecyltrimethylammonium bro-
mide (HTAB) and phospholipids have been monitored at a water-air interface
and in bulk media.631 Two kinds of aggregation processes were observed,
identified by three breaks at low lipid concentrations. The first process involved
the incorporation of the HTAB into the lipid vesicles and the subsequent
disruption of the vesicular structure leading to the formation of mixed micelles.
The second aggregation process indicated the completion of the mixed micelles
and the initiation of independent micelle formation process which was com-
pleted at the third stage. At higher concentrations of HTAB, no first stage was
observed owing to the presence of large vesicles. Mixed polyaromatic hydro-
carbon-surfactant solutions have been photochemically treated for surfactant
recovery,632 while the aggregation of a non-ionic surfactant Triton X has been
measured as a function of pressure using energy transfer between pyrene and
coumarin probes.633 Similar studies have been undertaken on water-soluble
oligomers, such as 1,4-bis[9 0 ,9 0 -bis(N,N,N-trimethylammonium)hexyl]-2 0 -fluor-
enyl]benzene tetraiodide,634 while a series of amphiphilic polyanions containing
9-carbazolylalkyl methacrylamide have been prepared and their fluorescence
properties examined in organic and aqueous media.635 Thus, whilst in organic
media only monomer emission was observed with no self-quenching, in water
fluorescence quenching was observed. In polyethylene oxide-polystyrene-poly-
ethylene oxide triblock amphiphilic copolymers, N,N-diethyldithiocarbamate
pendant sites have been incorporated that can react with benzyl radicals upon
irradiation to give locked polystyrene cores.636 Chemiluminescence from
luminol has been reduced by surfactants,637 while the colour change of
triphenylmethane dyes induced by surfactants at concentrations much greater
258 Photochemistry, 36, 2007, 232–298
than their CMCs are found to be accompanied by enhanced fluorescence.638

This is associated with the hydrophobic environment in the micelles preventing
non-radiative relaxation processes in the dyes. Thus, the more hydrophobic the
micelle the more fluorescence is observed. The low anisotropy values for a
poly(trifluoroethoxyphosphazine) and poly(ethyleneoxide) amphiphile has
been associated with the flexibility of the trifluoroethoxy group, allowing
enhanced rotational diffusion of the probe.639 Water-soluble nanospheres have
been made from dicarboxylic acids of poly(tert-butyl acrylate)-block-poly(2-
hydroxyethyl methacrylate),640 and a blob model has been used for studying
the dynamics of polymer segmental encounters as a function of time in near and
good solvents.641 Fluorescence depolarization kinetics have been used to
measure microviscosity changes in poly(ethylene oxide) and poly(propylene
oxide) triblock copolymers.642 At a 20% w/w concentration in solution,
although the viscoelastic modulus increased by an order of magnitude when
the sol-gel transition was crossed, the microviscosity of the hydrophilic medium
exhibited only minor changes. Also, faster and slower components of the
fluorescence depolarization were tentatively assigned to the dye in free solution
and associated in the micelles. CTAB micelles in the presence of hydroxy-
propyl-cyclodextrins have shown the presence of two types of micellar arrange-
ments.643 One was a pure surfactant micelle while the other was a surfactant
monomer complex with the cyclodextrin. Hydrogen bonding has been observed
between a photochromic multiplayer of assemblies of poly(4-vinyl pyridine)
and poly(acrylic acid),644 while luminescent polyelectrolytes have been pre-
pared by growing ZnO nanoparticles in a polyethylene matrix.645 Other studies
of interest include random ionomers of polystyrene,646 viscosity probes in
micelles using 4-hydroxycoumarin derivatives,647 microviscosity of polypropyl-
ene oxide melts,648 precipitation of polyethylene oxides in toluene649 and
development of a new PVC membrane for phosphates based on fluorescence
analysis.650
Optical studies on rare earth complexes as probes, and metal ions in general
in polymeric media, have been significant in the last year. Polystyrene contain-
ing mixed rare earth triisopropoxides undergoes complexation to yield a highly
fluorescent material with improved impact strength,651 whilst improved cation
selectivity has been obtained through the use of multilayer polyelectrolyte
membranes based on poly(acrylic acid)/poly(allylamine hydrochloride).652 Flu-
orescent composites have also been made based on poly(urethanes) with
samarium benzoate,653 Eu(III) and Tb(III) complexes in a sodium sty-
renesulfonate-ethylene glycol-sodium styrenesulfonate triblock copolymer654
and Eu(III) complexes in acrylate-styrene655 and acrylamide-acrylic acid656
systems. Hybrid macroporous silica materials have also been developed based
on monovacant Keggin-type polyoxometalates.657 Europium complexes with
polyester macroligands have been prepared to form heteroarm stars and
nanoscale assemblies,658 with a lamellar structure able to be thermally modi-
fied. Eu(III) with polymaleic acid forms a 1:1 complex659 with two different
environments, while with epoxy resins energy transfer has been observed from
the polymer to the complex.660 High quantum efficiencies for the Eu(III)
Photochemistry, 36, 2007, 232–298 259
complex were observed and have been discussed in many other applications.661
Lanthanide(III) methacrylate monomers have also been prepared,662 as have
Eu(III) polymers of styrene-acrylic acid.663 A ruthenium(II) tris(2,2 0 -bipyri-
dine) complex has been anchored to a polysiloxane matrix664 where one of the
ligands gave rise to a mobile metal centre. Quenching studies on anthracene
showed that mobilities and accessibilities were higher than for conventional
polysiloxanes. Fast energy transfer has been observed from carbazole block
copolymers to Ru(III) complexes.665 Nanosized micelles have also been made
from Ru(III) complexes with poly(styrene)-block-poly(vinyl pyridine) copoly-
mers666 wherein solution media disk and rod-like micelles could be formed.
Based on the amplified fluorescence quenching of polyquinolines, Ag(I) and
Hg(II) ions have been used as chemosensors,667 while polyurethane-CdS cured
complexes are useful membranes.668 Hexacyclane fluorophores undergo energy
transfer to rare earths,669,670 while phototunable systems have been made based
on 4,4 0 -conjugated[2,2 0 ]-bypridines complexed with various Zn(II), Hg(II) and
Re(VII) ions.671 A highly fluorescent and thermally stable complex has also
been prepared from Tb(III) ions with thienyltrifluoroacetone-elect-
ropolyrushthiol,672 while the same ions also complex well with poly(vinyl
sulfonate),673 displacing some six water molecules in the process. Here com-
plexation results in energy transfer, which is found to be inhibited in alcoholic
media but enhanced by the addition of ions such as salt. Here quantification of
the energy-transfer data allowed one to determine with a high degree of
accuracy the binding distance between the metal ions and the polymer chains.
Similar studies have been undertaken on Eu(III) with 4-vinylpyridine674 and
Ru(II) ions with a viologen containing poly(1-vinylimidazole).675
LC polymer systems continue to be developed for optical data recording
media. Polyurethane layers with good LC properties have been made,676 as
have template lyotropic LCs based on hydroxyethyl acrylate with dodecyltri-
methyl ammonium bromide.677,678 In the polymerization of the latter, lamellar
aggregates were found to form faster than either cubic or isotropic morph-
ologies owing to diffusional limitations on the growing chain. A statistical
theory has been developed to account for the compensating effect when
anchoring with two orthogonally photoaligned polymers.679 The data include
the angular dependence on the two aligned directions as well as a suitable
procedure for getting controlled anchoring strength in-situ. A theory has also
been developed for the fluorescence depolarization of a re-orientating molec-
ular probe in a mesophase with local uniaxial symmetry and a random
distribution of directors tilted with respect to the axis of the structure.680
Expressions were evaluated for the polarized fluorescence intensities as a
function of the cone opening as well as their dependency on the orientational
correlation functions and order parameters for both a uni- and a bi-axial probe.
Photoinduced molecular re-orientation and relaxation processes in a liquid
crystalline polymer have also been investigated in a series of pump-probe
experiments.681 Here both the frustration effect of the trans-cis photo-
isomerization transition on the nematic phase, and hence the photoinduced
isothermal transition from a perturbed nematic to a totally frustrated
260 Photochemistry, 36, 2007, 232–298
(isotropic) phase, and the approach of the glass transition were studied. The
elaboration and spectral properties of a passive broad-band reflector have also
been investigated.682 Photocrosslinkable chalcone polyimides undergo photo-
dimerization,683–685 while copolyester-imides emit blue light and operate as
effective LEDs.686,687 A case for a randon-field Ising model has been made
studying photoactive guest-non-photoactive host LC systems,688 while the LC
properties of diazadibenzoperylene dyes have been controlled by covalent and
hydrogen bonded attachment of mesogens.689 Polyoxetanes with active
4-cinnamoylbiphenyl mesogens show enantiotropic LC properties690 where
the spacer length influenced the thermal transitions and the nature of the
mesophase. The isotropization temperatures showed an even-odd effect as a
function of the spacer length. Main chain viologen polymers with organic
counterions have been found to exhibit either a high or low order smectic
phase.691 The LC temperature range was also influenced by the nature of the
counter ion, as were the fluorescence spectra. Thermotropic LC polyesters of
4,4 0 -biphenol and phenyl-substituted 4,4 0 -biphenols have been found to exhibit
very high thermotropic crystal-nematic transitions at 4501C when reacted with
terephthalic or naphthalenedicarboxylic acids,692 whereas the annealing of
films of polyacrylates with mesogen side-chains above their Tg gave significant
amplification of their photoinduced anisotropy.693 Triptycene groups have
been found to impart a high degree of solubility to PPVs, to form effective
nematic LCs.694 Here the conjugated backbones were found to align with the
direction of the nematic LC and can be re-orientated by the application of an
electric field. An intensity grating has been formed in an LC polymer with
azobenzene side groups through a photoinduced alignment of the mesogens,695
while smectic LC poly(methacrylates) with p-methoxyazobenzene groups gave
rise to photoinduced optical anisotropy upon irradiation to polarized light.696
On annealing, the polymers showed either out-of-plane or in-plane orientation,
depending upon the structure of the material. The concentraion of a photoin-
itiator has been found to influence the LC properties of a phenyletheracry-
late,697 whereas the encapsulation of monomer molecules in LC droplets
dispersed in a thermoplastic matirx can provide a convenient method to control
the orientation of LC directors.698 LC poly(1-alkynes) with biphenyl bridges
are also highly fluorescent in the near-UV.699
Continuing on from LC systems are photochromic materials, many display-
ing LC properties. Polymers of a special interest include thionines,700 multi-
functional acrylics,701 phthalocyanine hybrids of bisthienylene,702
diarylethenes,703 fluorinated naphthopyrans,704 cyclobutene-1,2-dione705 and
azo-polymers.706,707 Poly[oxy[trans-4-(2-phenylethenyl)pyridiniomethyl]-1,2-
ethanediyl chloride] undergoes trans-cis isomerization on irradiation, with
prolonged irradiation causing cycloaddition and then conversion to the original
linear oligomer.708 A novel polyamidoamine side-chain polyester with azoben-
zene motifs in the polymeric core has been found to display cis-trans isomer-
ization on light exposure,709 whereas polesters with 4-cyano-4 0 -
alkoxyazobenzene groups displays LC properties as well as a strong tendency
to aggregate.710 In this case the photoorientation effect is co-operative whereby
Photochemistry, 36, 2007, 232–298 261
the orientation of the chromic side-group induces alignment of the ester unit
and in-chain methylenes. Very high linear dichroism and birefringence are
observed and are unaffected by J-aggregation effects. In polynorbornenes with
azo groups, isomerization was found to depend upon the azo groups only and
not the polymer chain itself,711 whereas 2H-chromenes with pyranofluorenone
groups did not exhibit photochromism, whilst those with pyranofluorenols
did.712 Polyazophenols, on the other hand, have been found to isomerize very
slowly,713 while poly(vinyl alcohol) with azobenzene groups gives two mono-
layers, each exhibiting an alignment transition due to isomerization, with the
top layer have perpendicular rod-like structures.714 For polystyrene-b-poly(1,2-
isoprene-ran-3,4-isoprene) block copolymers with azobenzene side groups,
typical microphase separated morphologies such as sphere, cylinder and la-
mellar structures were observed.715 while dewar benzene groups on polyacrylics
did not hinder photoisomerization,716 whereas PMMA doped with zinc tetra-
benzoporphyrin produced a long-lived reversible triplet state.717 Hybrids in-
corporating triethoxysilane end-capped polyethylene glycols with tungsten
oxide have been prepared by a sol-gel process,718 while actuators have been
made from polydiacetylene with alkylurethanes.719 The latter undergoes a blue-
red phase shift on irradiation. Conjugated polymers with di-hetarylethene and
benzylidene-anthrone groups in the chain exhibit photoreversible magnetic
properties,720 whereas azobenzene-modified copolyaramides undergo reversible
light and heat induced trans-cis isomerization.721 In the latter case isomerizat-
ion-induced perturbations to the local dihedral angles residing in the atropiso-
metric binaphthylene main chain units serve as the genesis for the photo and
thermal regulated behaviour in these materials. Cationomers based on poly-
urethanes with nitroazobenzene groups have been shown to undergo photo-
isomerization with an irreversible photobleaching effect,722 whereas blends of
poly(pyridinium salts) give enhanced colour changes depending on the electron
withdrawing nature of groups on the polymer backbone.723 Polyanilines with
azobenzene sulfonic acid dopant form nanotubes which can undergo cis-trans
isomerization,724,725 while several polyurethanes with various azobenzene
groups exhibt birefringence properties,726–728 each with different growth pat-
terns depending upon the nature of the azobenzene group. Spirooxazines have
been looked at as usual. These include mercocyanine dyes729,730 where binding
to polysiloxanes only gave stability to the coloured form of the dye in solid
media and not in solution. Molecules with long alkyl groups731 and allyl
groups732 have also been made, with the latter exhibiting photochromism
between the two isomers of the coloured open form. Using quantum chemical
analysis, the pathways for ring opening show that the most stable mercocyanine
forms,733 TTC and CTC, can be obtained after C–O bond cleavage of the R and
S enantiomeric closed forms. The less stable mercocyanine forms, CTT and
TTT, revert to the corresponding closed form through an inversion mechanism
at the N1 0 nitrogen atom, and this explains the fast component of the kinetics of
the thermal fading reaction of the dye. Enantiomerization was achieved after
ring opening by cis-trans isomerization, either between two mercocyanines (i.e.,
TTC and CTC) or two s-cis intermediates. Apparently, the high energy barrier
262 Photochemistry, 36, 2007, 232–298
of the bond rotation necessary for the interconversion between TTC and CTC
isomers makes this process less favourable than the direct interconversion
between the s-cis intermediates (CCC and TCC). Thermal back reactions of
spirooxazines have also been calculated and measured in both solution and
poly(methacrylate) media.734 Azobenzene groups have been bound to numer-
ous acrylic polymers, with 29 mol-% of photochromic groups being required to
give a smectic phase.735 Changes in refractive index, restricted motions and
crosslinking effects have all been investigated on the photoisomerization.736–740
Aggregation in micelles and its effect on isomerization of azo groups has also
been probed.741–745 This includes sensitivity of absorption spectra, formation of
nanotubes, fabrication of multilayers through self-assembly processes, weak
anisotropy and reversibility. Spirobenzopyrans have also been investigated in
polymeric media.746,747 When copolymerized to N-isopropylacrylamide the
isomerization was found to be very slow, enabling the isomers to be separated
by water precipitation,746 while chelation gives some novel properties.747 Azo-
benzene groups have also been attached to polysiloxanes.748–751 These include
orientational control of alkyl chain lengths,748 microphase separation of cis-
isomeric molecules,749 packing and tail lengths in monolayers750 and broad
thermotropic properties.751 Photochromism in crown ethers is also possible.752–
755
Spironaphthoxazines when bound on the 6 0 -position of the naphthalene ring
exhibit bathochromic shifts in absorption spectra depending upon the metal
ion.752 Isomerization reduces the binding ability of metal ions. A new calixa-
crown ring has been synthesized753 where the kinetics of thermal decay are
biexponential, whereas dithiacrown ether styryl dyes form dimer complexes
capable of undergoing 2þ2 cycloaddition reactions.754 Reversible Z-E isomer-
ization also occurs, with an amphiphilic form giving relatively stable mono-
layers on water surfaces. Several other novel crown-ether systems have also
been discussed.755 Photochromism has also been reported for polymethine
dyes,756 Nile Red dye in dipalmitoylphosphatydilcholine surfactants,757 Erio-
chrome dyes758 and annulated coumarins.759 A number of articles have also
appeared on poly(acrylamides)760–762 where the isomerization reversibility is
very effective and useful for probing the effects of sol-gels.
4 Photodegradation and Photooxidation Processes in Polymers
The photodegradation of polymer materials continues to attract limited interest

although, as in the last few years, activity continues to decline. Thermal
degradation and stabilization processes rank much more highly in this partic-
ular field. Laser ablation processes continue to grow in interest with applica-
tions in electronics. A number of useful reviews on various aspects of the
subject have appeared, giving extensive coverage of techniques, applications
and mechanisms, and also numerous other topical articles of interest. Amongst
these are degradation processes in polyurethane adhesives,763 chemilumines-
cence and degradation processes,764 bond cleavages,765 activation spectra,766
polystyrenes,767 environmental issues,768 wavelength sensitivity,769
Photochemistry, 36, 2007, 232–298 263
biodegradability,770 the current status today771 and a general overview.772

Some specialist articles include photoradical ageing,773 identification and
quantification of processes,774–776 acceleration of processes,777 nature of light
sources,778 active intermediates,779 chemiluminescence for screening,780 weath-
ering of many polymers,781 product failure,782 electrooptical materials,783 melt
viscoelasticity,784 shopping bag problems in the environment785 and the value
and use of integrating spheres.786
4.1 Polyolefins. – Polyolefins continue to be widely investigated, with novel

submicrometric methods for thermal and infrared analysis being developed for
examining surface effects.787 A number of photodegradants continue to be
pursued, including ceric stearate,788 ferric stearate789,790 and ferric diet-
hyldithiocarbamate.791 Similar toughened polypropylene compounds were
found to behave differently with photoirradiation time,792 while photosensi-
tized degradation was induced by grafting with epoxidized lignosulfates,793 and
a high degree of stability achieved using sericite-tridymite-cristobalite
blends.794 Polyethylene improves the photostability of natural rubber in
blends,795 whereas under vacuum polypropylene degrades about 8 faster
than polyethylene under similar conditions of exposure.796,797 Oxygen acceler-
ates the photooxidation of polyethylene,798 while the application of an electric
fied improves its mechanical properties.799
4.2 Polystyrenes. – Through quantum yield measurements, the photooxida-

tion of polystyrene has been attributed to a photochain process, in the main
involving the dissociation of excited peroxides, whereas hydroperoxides are
shown to contribute to only 10% of the free radicals formed.800 In another
study on polystyrene hydroperoxides, benzaldehyde and hydroxyacetophenone
were identified as major products as well as some phenyl glycol.801 Mass
changes and crosslinking reactions have also been pursued,802,803 as has deg-
radation in tropical climates.804 Photodegradable blends of polystyrene and
carbon monoxide copolymers have also been found valuable for environmental
issues.805 On a similar note, recycled polystyrene degrades faster than virgin
material,806 and benzophenone, as expected, is also a powerful photosensi-
tizer.807 Photoproducts formed under natural and accelerated weathering con-
ditions have also been measured and compared.808
4.3 Poly(Acrylates) and -(Alkyl Acrylates). – Structured nanopore films of

poly(styrene-block-methyl methacrylate) copolymers have been made with
controlled spectral sensitivity, such that each block is sensitive to a specific
degradation wavelength.809 In copolymers of 2,2,2-trifluoroethyl methacrylate
with vinyl ethers, the photosensitivity is controlled by the vinyl ether units.810
Photodegradation occurs at the tertiary positions of the ether units followed by
lactone formation and chain scission processes. Furthermore, the fluorinated
side chains have been found to inhibit cyclization reactions.
264 Photochemistry, 36, 2007, 232–298
4.4 Poly(Vinyl Halides). – Poly(vinyl acetate) has been found to improve the
inherent light stability of PVC.811 The effect is apparently associated with an
efficient quenching of macro-radicals by low radicals formed in primary
photochemical stages in both phases. The carbonyl groups in the PVAc also
protect the polymer. Rare earth carboxylates photosensitize the degradation of
PVC but inhibit crosslinking reactions,812 while the addition of small amounts
of ferric and cobaltous chloride initially inhibit the photodegradation of PVC,
thereafter accelerating the process, but again the presence of the metal ions
prevents crosslinking reactions.813
4.5 Polyamides and Polyimides. – Rate constants for the decrease in the
intensity of the amide groups in a model nylon 6,6 compound have been
determined through pulsed laser Raman spectroscopy,814 while in side-chain
polyimides photobleaching processes have been measured.815 Simple models
were developed here, involving four different molecular states. Preferential
degradation of polyimide molecules has been found to occur under polarized
light exposure parallel to the direction of the UV light.816
4.6 Poly(Aromatics). – Poly(p-xylylene) undergoes photooxidation at the

methylene group, initially via hydrogen atom abstraction817 followed by attack
on the ring structure. Such instability prevents the long term use of this material
in outdoor applications. The backbone structures in PPVs influence the rates of
their photooxidation.818
4.7 Silicone Polymers. – The photolysis of an alternating copolymer of 2,6-

diethylene-acetophenone-disiloxane in the absence of oxygen resulted in com-
plete polymer recovery with no change in molecular weight, whereas in the
presence of oxygen significant chain scission was observed.819 In this case
hexamethyldisiloxane and 1,2-diacetylbenzene were formed as products.
4.8 Polyurethanes and Rubbers. – AFM analysis on photodegraded surfaces of

a polyurethane coating has identified blisters while under continuous exposure,
whereas under dark-light cycles the blisters retained a constant size and
shape.820 The former, as may be expected, was more damaging. In a polyocte-
namer evidence has been provided for the presence of low concentrations of
hydroperoxides being responsible for the photoinduced crosslinking.821 The
nature of the crosslinks, however, is disputed as being solely due to C–C or C–
O–C bonds. Using ATR-FTIR, the photodegradation of ABS has been found
to be heterogeneous down to a layer of 50 microns only.822 Carbonyl and
hydroxyl groups were readily observed, along with the disappearance of the
1,4-butadiene units. The butadiene units were the most severely degraded, with
the styrene-acrylic units remaining intact.
4.9 Polyesters. – Positron lifetime techniques have been used to measure

structural relaxation processes in irradiated poly(ethylene terephthalate)
(PET).823 Three relaxation processes with different kinetics were observed in
Photochemistry, 36, 2007, 232–298 265
irradiated material, compared with only two for the unirradiated polymer.
Photohydroxylation has been found to be a primary procees in the photoox-
idation of PET fibres,824 while DSC analysis of photooxidized PET films
showed the reformation of crystalline regions associated with the re-alignment
of amorphous material.825 Contaminated water in PET bottles has been found
to be destroyed only after some 5-6 hours of sunlight exposure.826 The bio- and
photodegradabilities of aliphatic and aromatic polyesters have also been
investigated in terms of physical mechanical property changes.827
4.10 Photoablation of Polymers. – Structural relaxation and electron-phonon

interactions have been investigated during the photochemical hole-buring of
several polymer systems.828 In porphyrin containing DNA-lipid complexes,
marked hole broadening was observed but no hole filling at 40 K, owing to
intercalation of the porphyrin molecules into the double helix of the DNA.
Dendrimer porphyrin neat films showed sharp holes at 20 K, with a higher
generation exhibiting good thermal stability due to effective surface mobility.
Doped PMMA and polystyrene films have been optimized for laser ablation
work.829 Here the importance of employing relatively strongly absorbed wave-
lengths in laser processing relates, besides the efficient etching and good surface
morphology, to the minimization of the chemical modifications. In contrast, it
is claimed that pulsed irradiation work is highly disadvantageous with regard to
the chemical integrity of the substrate. PTFE surfaces have enhanced adhesion
to copper plates following ArF excimer laser ablation under a hydrazine and
ammonia atmosphere.830 Other adhesion promoters include the use of acry-
lated photoinitiators.831 Synchrotron radiation has been used to crosslink
PTFE,832 and the real-time evolution of luminescence properties of ion-irradi-
ated polymer films has been investigated by means of ion-beam induced
luminescence measurements.833 Marked narrowing of spectral holes in dyed
polymer films has been observed through the use of spectral hole burning under
high pressures.834 Under Xe2 excimer laser ablation, polycarbonate material
undergoes severe surface roughening followed by the evolution of chemical
functional groups due to the severing of aromatic C–C and carboxylic
groups.835 Polymers have been categorized into those with low, medium and
high fluency for laser ablation.836,837 Polymers with triazine groups were found
to have the lowest threshold for ablation.
4.11 Natural Polymers. – Camphorquinone is a sensitizer in cellulose fibres,838

while wood flour is a good filler and stabilizer for PVC.839 Pine wood lignin
gives primarily cis-sinapyl alcohol and sinapyl aldehyde on irradiation, asso-
ciated with oxidation of the guaiacyl units.840 Wood pulp treated with hydro-
gen periodide has been examined by laser flash photolysis,841 while acetylated
and bleached aspen chemithermomechanical pulp have been examined through
the use of UV-visible diffuse reflectance spectroscopy.842,843 It was concluded
that light-induced yellowing was not excusively an oxygen aided process, and in
fact in an oxygen saturated atmosphere it impaired the yellowing process. In a
similar fashion acid anhydrides also inhibited the yellowing of fir sapwoods in
266 Photochemistry, 36, 2007, 232–298
the order phthalic 4 maleic 4 succinic 4 acetic 4 butyric anhydride.844

Hydrogenolysis of lignin also eliminated yellowing.845 Hydroxyl radicals have
been found to be the prime cause of initiating the degradation of glucosidic
units,846 and again guaiacyl units are found to be more degradable than
syringyl units.847
4.12 Miscellaneous Polymers. – UV photolysis of methoxylated melamine

formaldehyde gives methyl radicals followed by more stable methane radicals,
brought about by side-chain reactions,848 while acrylic-melamine coatings
undergo primarily hydrolysis under irradiation conditions with high humid-
ity.849 The degree of degradation of cellulose triacetate decreases with enzyma-
tic degradation,850 while polycarbonate undergoes loss of optical properties on
irradiation owing to a photo-Fries rearrangement and oxidation processes.851
High humidity also caused photobleaching of the yellowing in polycarbonates.
Vinyl ester composites undergo severe degradation when exposed to UV light,
with changes in surface chemistry, morphology and the bulk matrix,852 whereas
quinine-methides formed from phenolic antioxidants in polymer materials are
photobleached with UV light.853 Thermosetting acrylic clearcoats undergo loss
of functional groups with the concommitant formation of carboxyl and
hydroxyl groups,854 as do acrylic-urethane clearcoats.855,856 Surface weathering
has been studied in glycol acrylate composites,857 epoxy matrices858 and
poly(vinyl methyl ether).859 Other studies of interest include photodegradation
of PTFE,860 shopping bags,861 poly(pyridinium salts),862 calcium carbonate
doped polymers,863 recyclable materials864 and polyimides.865 A new method
has been developed for measuring chain scissions in polymer degradation,866
and a model developed for linking field and laboratory trials.867
5 Photostabilization of Polymers
Photostabilization processes have not received much attention in the last year
other than a multitude of review and specialist industrial articles. These include
stabilization of polypropylene fibres,868 new stabilizer developments,869–882
sorting of stabilizers for polyethylene,883 trends in UV absorbers,884 hindered
piperidines (HALS) for polyacrylics885 and urethanes,886 new stabilizers for
polyolefins,887 enhanced service-life applications,888 stabilizer masterbatches
for polyester,889 stabilizers for UV-cured acrylic overcoats for PVC890 and
stabilization of clearcoats and various commercial packages.891
Apparently, pre-irradiating polyethylene containing a HALS with a low
pressure Hg lamp imparts some surface stabilization toward sunlight expo-
sure.892 Anthracene-HAS stabilizer molecules are found to be more effective
stabilizers than the separate molecular moieties,893 while the nature of the
polymer composition affects the distribution of nitroxyl radicals in stabilized
materials.894 Polyethylene with terminal HAS groups has been found to be very
light stable,895 as were reactive acrylic coatings with acrylated HAS systems.896
A new epoxide amine based HAS has been found to be quite effective in
Photochemistry, 36, 2007, 232–298 267
stabilizing PP,897 as was a new rubber grafted maleic anhydride HAS system.898
Cyclic bridged amines are also effective co-synergists with HAS,899 as are
lactones.900 The polymer matrix has been found to influence the excited state
properties of UV absorbers,901 while novel effective adducts of HAS and
2-hydroxyphenylbenzotriazoles have been made.902
UV absorbers have been shown to undergo photolysis reactions in polymer
materials, the loss being quite critical, depending upon the nature and form of
the material.903 Spectroscopic methods have been developed to design more
effective UV absorbers which function via intramolecular proton-transfer in
the excited state.904 Other effective stabilizers for polymers includes thioureas
for PMMA,905 aryl nitrenes for PP,906 diphenylnitrone for polyethylene,907 zinc
glycerolate in PVC908 and hexazoclanes for cellulosics and nylons.909
6 Photochemistry of Dyed and Pigmented Polymers
Dye and pigment fading and sensitization continue to be highly active areas of
interest, especially with regard to photocatalytic chemistry. The sensitized
production of singlet oxygen is known to play an important role in polymer
oxidation reactions with dyes. Zinc phthalocyanine sulfonate is widely used to
chemically treat dyed fibres as a sterilizing treatment in washing powders.910 It
was found to be detrimental to the photostability of a range of dyestuffs on
different fibres after a washing treatment. Singlet oxygen production and
hydroperoxide formation were key steps in the enhanced photofading of the
dyes. The addition of a hydroxyl KSCN radical scavenger was found to impair
the photofading process. The photooxidation of three new bicycle-boron
dipyrromethane difluoride dyes depended upon the nature of the solvent,911
while for a series of vat dyes in cellulose photofading was found to occur mainly
by oxidation in dry fabric, whereas in wet fabric under anaerobic conditions
fading occurred through a photoreductive process to the leuco form of the
dye.912 Intramolecular triplet energy transfer is an important process in con-
trolling the photostability of many dyes,913 which may also be induced through
the use of absorbers.914 Singlet oxygen is a common species in dye photofading
chemistry, with basic dyes such as Crystal Violet being a noteable example.
Here the use of absorbers is found to be ineffective against fading, whilst nickel
quenchers improve against the fading significantly.915 Azo dyes have also been
co-reacted with stabilizer moieties for enhanced stabilization,916 while Rhoda-
mine 6G dye has been copolymerized with 1,8-naphthalimide derivatives.917
Photo-Fenton reagent was used to sensitize the photofading of Malachite
Green dye in the presence of various aromatic compounds.918 The compounds
did not influence the type of degradation pathways, just the rate process, which
primarily involved OH and N-demethylation cleavage. Using molecular orbital
analysis and fading reactions, cyanine dyes have also been found to photofade
via a singlet oxygen reaction mechanism.919 Acidic pH conditions have been
found to enhance the photofading of an Acid Blue 25 anthraquninone dye in
nylon 6,6 film.920 This process is already well-known and associated usually
268 Photochemistry, 36, 2007, 232–298
with protonation of the dye and enhanced potential for hydrogen-atom ab-
straction. Photo and molecular transformation processes of methyl red in PVA
film on laser irradiation have been investigated,921 while in another article dye
fading has been considered based on singlet oxygen and aggregation effects.922
Carthamin dye in cellulose triacetate film also fades via a singlet oxygen
mechanism and is inhibited by nickel quenchers.923 Factors influencing the
photofading of vat dyes have been determined, especially those related to the
dye bath operation,924,925 while certain phthalocyanine dyes have been found to
emit intense singlet oxygen sensitized delayed fluorescence upon laser irradia-
tion in oxygen.926 The photofading of azo dyes varies with the type of added
heterocycle, such as furan or thiophene,927 whereas a disperse yellow dye was
found to fade faster when in a less aggregated form.928 Multifilament nylon 6
yarns are found to photodegrade faster than single filaments,929 and the Blue
Wool ISO standard scale of lightfastness measurement has been found to
depend significantly upon the nature of the light source used for weathering.930
Numerous articles of a general interest have appeared on photocatalytic
chemistry. These include nanoparticles,931 protection of buildings,932–934 antibac-
terial properties,935 ageing of pigment blends,936 modified titanium dioxides,937
photocatalytic paints,938 stabilization of pigmented systems,939 sensitization of
acid dyes940 and clay masterbatches.941 Anatase has been found to have a
detrimental effect on the light stability of inks,942 while similar effects have been
prevented by encapsulating dyes in polymers.943 In PVC, titanium dioxide has a
catalytic effect due to its semiconductor properties,944 whereas in paper systems
titania supported in an inorganic fibre matrix gives good stabilization.945 Tita-
nium dioxide also photosensitizes the degradation of plasticizers in PVC, with
carbon dioxide being the major breakdown product.946 The latter has also been
used as a monitor for the photooxidation rates of titania filled alkyd paint
films.947 Here degradation rates were found to increase with increasing humidity.
In polyethylene film, nanoparticle uncoated titanium dioxide pigments have been
shown to be more photoactive than pigmentary grades and operate as powerful
prooxidants during prior processing generating hydroperoxides and carbonylic
groups.948 The same behaviour is operative in alkyd based paint films, with SEM
analysis showing deep pits being formed around the nanoparticles. Pigment
activity was also related to charge-carrier generation properties as measured by
dielectric microwave spectroscopy. In acrylic and isocyanate based paint films,
coated nanoparticles of titanium dioxide have been shown to be powerful UV
absorbers above 350 nm, and during weathering can outperform commercial
HAS and UV absorber stabilizers.949 The nanoparticles were also found to
antagonize the stabilizing effect of HAS, while in wood coatings the nanoparticles
were found to be excellent inhibitors of colour formation, owing to their sensi-
tizing effect in photobleaching the lignin by-products.
References
1. J.P. Fouassier (ed.), Research Trends, Trivandrum, India, 2001, 190 pp.
2. J.P. Fouassier, Recent Res. Dev. Photochem. Photobiol., 2000, 4, 51.
Photochemistry, 36, 2007, 232–298 269
3. J. Paczkowski and D.C. Neckers, Electron Transfer in Chemistry, 2001, 5, 516.

4. W. Cao, Gaofenzi Tongbao, 2002, 1, 1.
5. T. Motoyama, Setchaku, 2001, 45, 337.
6. S. Herold, Adhesives Age, 2001, 44, 27.
7. K. Rhodes, Adhesives Age, 2001, 44, 22.
8. Y. Yang, Reguxing Shuzhi, 2001, 16, 22.
9. M.D. Goodner and C.N. Bowman, Chem. Eng. Sci., 2002, 57, 887.
10. A. Muhlebach, P.A. Van Der Schaaf and A. Hafner, NATO Sci. Ser., II: Maths,
Phys. Chem., 2002, 117.
11. C. Decker, Pigment Resin Technol., 2001, 30, 278.
12. T. Corrales, F. Catalina, C. Peinado, N.S. Allen, A.M. Rufs, C. Bueno and
M.V. Encinas, Polymer, 2002, 43, 4591.
13. M.V. Encinas, T. Corrales, F. Catalina, C. Peinado, A.M. Rufs, K. Schmith,
M.G. Neumann and N.S. Allen, Polymer, 2002, 43, 3909.
14. H. Li and W. Yang, Beijing Huagong, 2001, 28, 45.
15. C. Valderas, S. Bertolotti, C.M. Previtali and M.V. Encinas, J. Polym. Sci., Part A:
Polym. Chem. Ed., 2002, 40, 2888.
16. I. Erel, I. Cianga, E. Serhatli and Y. Yagci, Eur. Polym. J., 2002, 38, 1409.
17. S.A. Chesnokov, V.K. Cherkasov, G.A. Abakumov, O.N. Mamysheva,
Y.V. Chechet and V.I. Nevodchikov, Kobunja Kwahak Kwa Kisul, 2001, 50, 2366.
18. M. Ying, C. Barner-Kowolik, J.P.A. Heuts and T.P. Davies, Eur. Coatings
J., 2000, 1, 44.
19. N. Oz and A. Akar, J. Appl. Polym. Sci., 2002, 83, 2494.
20. M.L. Shekta and O.V. Suberlyak, Ukrainskii Khimicheskii Zhurnal, 2002, 68, 117.
21. E. Novikova, A. Kolendo, V. Syromyatnikov, L. Avramenko, T. Prot and
K. Golec, Polimery, 2001, 46, 406.
22. A.F. Maslyuk, S.A. Kudinov, G.K. Bereznitskii, N.A. Shikhanova, D.B. Shakh-
min and E.V. Prokopova, Ukrains’kii Biokhimichnii Zhurnal, 2002, 74, 56.
23. C. Grotzinger, D. Burget, P. Jacques and J.P. Fouassier, Macromol. Chem. Phys.,
2001, 202, 3513.
24. H.G. Woo, B.H. Kim, M.S. Cho, D.Y. Kim, Y.S. Choi, Y.C. Kwak, H.S. Ham,
D.P. Kim and T.S. Hwang, Bull. Korean Chem. Soc., 2001, 22, 1337.
25. H. Yamashita, K. Yoshizawa, M. Ariyuki, S. Higashimoto and M. Anpo, Studies
Surf. Sci. Catal., 2002, 141, 495.
26. A. Maliakal and N.J. Turro, Polym. Mater. Sci. Eng., 2002, 87, 166.
27. M. Degirmenci, I. Cianga and Y. Yagci, Macromol. Chem. Phys., 2002, 203, 1279.
28. L. Macarie, I. Manoviciu, V. Manoviciu, G. Dehelean, G. Ilia, S. Iliescu, A. Popa
and N. Pleasu, Polymer, 2000, 42, 1825.
29. M. Degirmenci, G. Hizal and Y. Yagci, Macromolecules, 2002, 35, 8265.
30. A. Wrzyszczynski and H. Janota, Polymery, 1996, 41, 560.
31. I.R. Gould, D. Shukla, D. Giesen and S. Farid, Helv. Chim. Acta, 2001, 84, 2796.
32. J. Kabatc, M. Pietrzak and J. Paczkowski, J. Chem. Soc., Perkin Trans. 2, 2002, 2, 287.
33. R. Jantas, T. Wodka and G. Janowska, Polymery, 2001, 46, 812.
34. S.H. Qin, D. Qin and K.Y. Qiu, Chin. J. Polym. Sci., 2001, 19, 441.
35. Q. Gao, Z. Liu, H. Guan, G. Yang and X. Yu, Chemical Research in Chinese
Universities, 2002, 18, 56.
36. S. Mah, D. Koo, H. Jeon and S. Kwon, J. Appl. Polym. Sci., 2002, 84, 2425.
37. R.E. Medsker, A. Sebenik and H.J. Harwood, Polym. Bull., 2002, 48, 17.
38. M.L. Gomez, R.E. Palacios, C.M. Previtali, H.A. Montejano and C.A. Chesta,
J. Polym. Sci., Part A: Polym. Chem. Ed., 2002, 40, 901.
270 Photochemistry, 36, 2007, 232–298
39. I.A. Banerjee, G.A. Epling and N.K. Modukuru, Surf. Coatings Int., 2002, 38,
2383.
40. G. Bianco and M.H. Gehlen, J. Photochem. Photobiol., Chem. Ed., 2002, 149, 115.
41. Q. Xi, Z. Lu and K. Yang, Mol. Cryst. Liq. Cryst. Sci. Technol., Sect. A: Mol.
Cryst. Liq. Cryst., 2001, 371, 9.
42. R.J. Lee, J.J. Lin and S.S. Lin, Polym. Prep. (Am. Chem. Soc., Div. Polym. Chem.),
2002, 43, 934.
43. C.S. Pinzino, C.C. Chappelow, A.J. Holder, J.A. Morrill, C.D. Harris,
M.D. Power and J.D. Eick, J. Appl. Polym. Sci., 2002, 85, 159.
44. J. Park, Korean Polym. J., 2001, 9, 206.
45. Y. Hua and J.V. Crivello, Chem. Mater., 2002, 14, 2369.
46. A. Shirai, H. Kubo and E. Takahashi, J. Photopolymer. Sci. Technol., 2002, 15, 29.
47. M. Degirmenci, A. Onen, Y. Yagci and S.P. Pappas, Polym. Bull., 2001, 46, 443.
48. D.M. Vuluga, D.S. Vasilescu and M.J.M. Magdalena, Polym. Bull., 2002, 47, 485.
49. M.R. Rodrigues and M.G. Neumann, Macromol. Chem. Phys., 2001, 202, 2776.
50. M. Degirmenci, Y. Hepuzer and Y. Yagci, J. Appl. Polym. Sci., 2002, 85, 2389.
51. J. Choi, S. Kwon and S. Mah, J. Appl. Polym. Sci., 2002, 83, 2082.
52. W. Zhou, S.M. Kuebler, D. Carrig, J.W. Perry and S.R. Marder, J. Am. Chem.
Soc., 2002, 124, 1897.
53. T. Sato, R. Maeda, M. Seno and T. Hirano, Eur. Polym. J., 2002, 38, 1491.
54. H.Y. Moy, P.Y. Chow, W.L. Yu, K.M.C. Wong, V.W.W. Yam and L.M. Gan,
Chem. Commun., 2002, 9, 982.
55. C.R. Rivarola, S.G. Bertolotti and C.M. Previtalli, J. Polym. Sci., Part A: Polym.
Chem. Ed., 2001, 39, 4265.
56. Y. Toba, Kobunshi Ronbunshu, 2002, 59, 449.
57. F. Kasapoglu, A. Onen, N. Bicak and Y. Yagci, Polymer, 2002, 43, 2575.
58. F. Kasapoglu and Y. Yagci, Macromol. Rapid Commun., 2002, 23, 567.
59. S. Yurteri, A. Onen and Y. Yagci, Eur. Polym. J., 2002, 38, 1845.
60. K. Ren, J.H. Malpert, H. Gu, H. Li and D.C. Neckers, Tetrahedron, 2002, 58,
5267.
61. V. Andrulevicute, R. Lazauskaite, J.V. Grazulevicius and A. Stanisauskaite,
J. Photochem. hotobiol., Chem. Ed., 2002, 147, 63.
62. W.G. Kim, H.K. Ahn, H.W. Lee, S.H. Kim and J.V. Crivello, Opt. Mater., 2002,
21, 343.
63. M. Sangermano, G. Malucelli, R. Bongiovanni, A. Priola, U. Annby and
N. Rehnberg, Eur. Polym. J., 2002, 38, 655.
64. J. Liu, T. Wang and Y. Huang, Ganguang Kexue Yu Guang Huaxue, 2002, 20, 177.
65. M. Sangermano, S.N. Falling and J.V. Crivello, J. Macromol. Sci., Pure Appl.
Chem., 2002, A39, 1265.
66. C. Decker, C. Bianchi, D. Decker and F. Morel, Prog. Org. Coatings, 2001, 42,
253.
67. M. Sakai, M. Ichida and A. Nakamura, AIP Conf. Proc., 2001, 590, 451.
68. V.A. Karachevtsev, O.M. Vovk, A.M. Plochotnichenko and A.V. Peschanskii,
AIP Conf. Proc., 2002, 633, 17.
69. M. Suzuki, AIP Conf. Proc., 2001, 590, 401.
70. Y. Okawa and M. Aono, RIKEN Rev., 2001, 37, 3.
71. T. Yaji, K. Izumi and S. Isoda, Appl. Surf. Sci., 2002, 188, 519.
72. L.A. White, C.E. Hoyle, S. Jonsson and L.J. Mathias, J. Polym. Sci., Part A:
Polym. Chem. Ed., 2002, 40, 694.
73. R. Saint-Loup and B. Ameduri, J. Fluorine Chem., 2002, 116, 27.
Photochemistry, 36, 2007, 232–298 271
74. W.S. Lyoo and W.S. Ha, Fibres on Polymers, 2001, 2, 108.
75. J. Lange, N. Davidenko, J. Rieumont and R. Sastre, Polymer, 2002, 43, 1003.
76. J.Y. Chang, K. Seo, H.J. Cho, C.J. Lee, C. Lee, Y. Kang and J. Kim, Macromol.
Res., 2002, 10, 204.
77. C. Yu, M. Xu, F. Svec and J.M.J. Frechet, J. Polym. Sci., Part A: Polym. Chem.
Ed., 2002, 40, 755.
78. T. Yamamoto, T. Saso, A. Kajiwara and M. Kamachi, Macromol. Symp., 2002,
179, 331.
79. R. Maruyama, M. Maniruzzaman, S. Kawaguichi and K. Ito, Macromol. Symp.,
2002, 179, 133.
80. D.C. Sherrington, A.T. Slark and K.A. Taskinen, Makromol. Chem. Phys., 2002,
203, 1427.
81. Y.Z. You, C.Y. Hong, R.K. Bai, C.Y. Pan and J. Wang, Macromol. Chem. Phys.,
2002, 203, 477.
82. S. Harrisson, T.P. Davis, R.A. Evans and E. Rizzardo, Macromolecules, 2002, 35,
2474.
83. S. Shoji, S. Kawata, A.A. Sukhorukov and Y.S. Kivshar, Opt. Lett., 2002, 27, 185.
84. A.P. Alexandrov, S.V. Muraviov, N.A. Babina and N.M. Bityurin, Proc. SPIE,
2001, 4423, 74.
85. M. Gaboyard, Y. Hervaud and B. Boutevin, Polym. Int., 2002, 51, 577.
86. T.G. Gerasimov and D.L. Snavely, Macromolecules, 2002, 35, 5796.
87. S. Blaya, L. Carretero, R.F. Madrigal and A. Fimia, Appl. Phys. B: Lasers Opt.,
2002, 74, 243.
88. A.V. Kutsenova, P.P. Levin and V.B. Ivanov, Vysokomol. Soedin, Ser A, Ser. B.,
2002, 44, 733.
89. Y. Matsuura, K. Matsukawa, R. Kawabata, N. Higashi, M. Niwa and H. Inoue,
Polymer, 2001, 43, 1549.
90. M.D. Hseih and E.T. Zellers, Sensors Actuators, B: Chem., 2002, 82, 287.
91. I. Naito, Y. Fujimura, S. Kobayashi and M. Kotani, J. Photopolym. Sci. Technol.,
2002, 15, 97.
92. R. Jantas and H. Szocik, Polym. Bull. (Berlin), 2002, 48, 105.
93. D.W.P.M. Loewik, J.G. Lindhart and Jan C.M. van Hest, Polym. Prep. (Am.
Chem. Soc., Div. Polym. Chem.), 2002, 43, 384.
94. S.V. Ryabov, N.S. Allen, M. Edge, S.N. Kobylinskii, A.A. Pokholenko and Z.V.
Voitenko, Dopovidi Natsional’noi Akademii Nauk Ukraini, 2002, 2, 156.
95. N. Kizilcan and A. Akar, J. Appl. Polym. Sci., 2002, 85, 500.
96. L. Macarie, G. Dehelean, G. Ilia, S. Iliescu, A. Popa and L. Pacureanu, Rev. Chim.
(Bucharest), 2001, 52, 748.
97. W.D. Davies, F.D. Jones, J. Garrett, I. Hutchinson and G. Walton, Surf. Coatings
Int., Part B: Coatings Trans., 2001, 84, 213.
98. T. Jung and R. Jahn, Farbe Lacke, 2002, 108, 24.
99. J.H. de Groot, K. Dillingham, H. Deuring, H.J. Haitjema, F.J. van Beijma,
K. Hodd and S. Norrby, Biomacromolecules, 2001, 2, 1271.
100. V. Castelvetro, M. Molesti and P. Rolla, Macromol. Chem. Phys., 2002, 203, 1486.
101. X. Allonas, J.P. Fouassier, L. Angiolini and D. Caretti, Helv. Chim. Acta, 2001, 84,
2577.
102. J. Jakubiak, A. Sionkowska, L.A. Linden and J.F. Rabek, J. Therm. Anal.
Calorim., 2001, 65, 435.
103. C. Iojoiu, V. Harabagiu, M. Pinteali, M.J.M. Abadie and B.C. Simionescu,
J. Macromol. Sci. Pure Appl. Chem., 2002, A39, 467.
272 Photochemistry, 36, 2007, 232–298
104. J.B. Hutchinson, C.J. Craig and K.S. Anseth, Polym. Prep. (Am. Chem. Soc., Div.
Polym. Chem.), 2002, 43, 730.
105. I.C. Alupei, V. Alupei and H. Ritter, Macromol. Rapid Commun., 2002, 23, 55.
106. W. Xu, J. Yang, Z. Zeng and Y. Chen, Gongneng Gaofenzi Xuebao, 2002, 15, 127.
107. F. Scigalaski and J. Paczkowski, Polimery, 2001, 46, 613.
108. M. Tsnooka, T. Yamamoto, Y. Kurokawa, K. Suyama and M. Shirai, J. Photo-
polym. Sci. Technol., 2002, 15, 47.
109. E. Polo, A. Barieri, S. Sostero and M.L.H. Green, Eur. J. Inorg. Chem., 2002, 2, 405.
110. R. Dabestani and I.N. Ivanov, Int. SAMPE Symp. Exhib., 2001, 46, 2075.
111. Y. Xie, P. Liu, R. Ji and Z. Li, Hebei Gongye Daxue Xuebao, 2002, 31, 67.
112. T.L. Edwards, S.K. Mohanty, A.B. Frazier, R.K. Edwards and C.L. Thomas, Ann.
Tech. Conf.– Soc. Plast. Eng., 59th, 2001, 3083.
113. J.V. Crivello, Radiat. Phys. Chem., 2002, 63, 21.
114. W.H. Heath, P.I. Tattersall, C.L. McAdams and W.C. Grant, Polym. Mater. Sci.
Eng., 2002, 87, 405.
115. Y. Bai, P. Chiniwalla, P.A. Kohl and S.A. Bidstrup-Allen, Proc. Int. Symp. Adv.
Packaging Mater.: Proc., Prop. Interfaces, Braselton, GA, USA, March 11-14th,
2001, 322.
116. G. Malucelli, Y. Chen, A. Priola, R. Bongiovanni and M. Sangermano, Mater.
Eng., (Modena, Italy), 2002, 13, 99.
117. J.V. Crivello and R.A. Ortiz, J. Polym. Sci., Part A: Polym. Chem. Ed., 2002, 40,
2298.
118. E. Takahashi, F. Sanda and E. Takeshi, J. Polym. Sci., Part A: Polym. Chem. Ed.,
2002, 40, 1037.
119. Y. Huang, J. Liu, T. Wang and H. Liu, Ganguang Kexue Yu Guang Huaxue, 2002,
20, 88.
120. Z. Gomurashvili and J.V. Crivello, Macromolecules, 2002, 35, 2962.
121. F. Cazaux and X. Coqueret, Surf. Coatings Int., Part B: Coatings Trans., 2001, 84,
127.
122. H. Li, K. Ren and D.C. Neckers, Macromolecules, 2001, 34, 8637.
123. J. Simokaitiene, R. Lazauskaite and J.V. Grazulevicus, J. Photochem. Photobiol.,
Part A: Chem. Ed., 2002, 147, 55.
124. S. Katogi and M. Yusa, J. Photopolym. Sci. Technol., 2002, 15, 35.
125. A. Carroy, S. Ilg and T. Bolle, Paint India, 2002, 52, 71.
126. H. Okamura, S. Toda, M. Tsnooka and M. Shirai, Tetrahedron, 2002, 40, 3055.
127. A.F. Maslyuk, G.K. Bereznitskii, D.B. Shakhnin, D.B. Shikhanova and
S.A. Kudinov, Dopovidi Natsional’noi Akademii Nauk NAN Ukraini, 2002, 4, 157.
128. (a) Y. Shindo, Y. Yamad, J. Kawanobe and K. Inoue, J. Photopolym. Sci.
Technol., 2002, 15, 153; (b) Y. Shindo, Y. Yamad, J. Kawanobe and K. Inoue,
J. Photopolym. Sci. Technol., 1999, 1, 147.
129. Z. Gan, S. Huang and H. Xie, Huazhong Keji Daxue Xuebao Ziran Kexueban,
2001, 29, 106.
130. T.D. Kim, H.M. Bae and K.S. Lee, Bull. Korean Chem. Soc., 2002, 23, 1031.
131. M.H. Lee, Y.S. Cheong and M.S. Gong, Korean Polym. J., 2001, 9, 327.
132. B. Yao and X. Xiaoling, Wuxi Qinggong Daxue Xuebao, 2001, 20, 619.
133. C.D. Vo, D. Kuckling, H.J.P. Adler and M. Schonhoff, Colloid Polym. Sci., 2002,
280, 400.
134. D. Kuckling, M. Harmon and C.W. Frank, Macromolecules, 2002, 35, 6377.
135. T. Oyama, T. Takeshi, K. Ebitani, M. Hoshino, T. Iijima and M. Tomoi, React.
Funct. Polym., 2001, 49, 99.
Photochemistry, 36, 2007, 232–298 273
136. B.J. Qu, Chin. J. Polym. Sci., 2002, 20, 291.

137. Q. Wu and B. Qu, J. Appl. Polym. Sci., 2002, 85, 1581.
138. W. Schinner and T. Wolff, Colloid Polym. Sci., 2001, 279, 1225.
139. T.M.R. Miranda, A.R. Goncalves and M.T.P. Amorim, Polym. Int., 2001, 50,
1068.
140. S.W. Fang, H.J. Timpe and A. Gandini, Polymer, 2002, 43, 3505.
141. X. Zhang and J. Qiu, Xiandai Suliao Jiangong Yingyong, 2001, 13, 5.
142. X. Shen and J. Wang, Zhongguo Suliao, 2001, 15, 65.
143. A.V. Shyichuk and G.V. Tokaryk, Kompozitsiini Polimerni Materiali, 2000, 22, 104.
144. M. Shirai, K. Yazama, H. Okamura, M. Tsnooka, H. Watanabe and T. Itani,
J. Photopolym. Sci. Technol., 2000, 42, 645.
145. C.P. Chwang, S.N. Lee, Y.M. Kuo, S. Chao and D.Y. Chao, Polym. Adv. Technol.,
2002, 13, 293.
146. R.S. Lee and J.M. Yang, Polym. J., 2002, 34, 247.
147. V.V. Mogil’nyi and A.I. Stankevick, J. Opt. Technol., 2002, 69, 1.
148. M. Li, Y. Qin, Z. Chang and E. Wang, Ganguang Kexue Yu Guang Huaxue, 2002,
20, 247.
149. C. Decker, T. Viet and T. Nguyen, J. Appl. Polym. Sci., 2001, 82, 2204.
150. V.V. Semenov, E. Yu. Ladilina, N.F. Cherepennikova and T.A. Chesnokova,
Russ. J. Appl. Chem., 2002, 75, 127.
151. X. Yao, C.X. Li and Q.G. Wang, Huaxue Yanjiu, 2002, 13, 21.
152. E. Krendlinger, H. Ebrhardt, F.L. Heinrichs and H. Endres, Farbe Lacke, 2002,
108, 26.
153. J.H. Bae, M.S. Choi, W.G. Kim, Y. Kwon and J.Y. Lee, Mol. Cryst. Liq. Cryst.
Sci., Technol. Sect. A: Mol. Cryst. Liq. Cryst., 2002, 377, 313.
154. A.M. Ferretti, G. Costante and A. Ponti, Res. Chem. Intermed., 2002, 28, 159.
155. J.B. Hutchinson, K.T. Haraldsson, C.J. Hawker and C.N. Bowman, Polym.
Mater. Sci. Eng., 2002, 87, 162.
156. C. Khoury, G.A. Mensing and D.J. Beebe, Lab on a Chip, 2002, 2, 50.
157. M. Mizutani, S.C. Arnold and T. Matsuda, Biomacromolecules, 2002, 3, 668.
158. H. Lu, L.G. Lovell and C.N. Bowman, Macromolecules, 2001, 34, 8021.
159. B. Philip and K. Sreekumar, Eur. Polym. J., 2002, 38, 2441.
160. T. Baldacchini, H. Chen, R. Farrer, M. Previte, J. Moser, M. Naughton and
J.T. Fourkas, Proc. SPIE., 2002, 4633, 136.
161. J.F.G.A. Jansen, A.A. Dias, M. Dorschu and B. Coussens, Macromolecules, 2002,
35, 7529.
162. G. Zhang and Y. Huang, Xianweisu Kexue Yu Jishu, 2001, 9, 1.
163. M. Ukon, T. Sugino, T. Watanabe, H. Monobe and Y. Shimizu, Macromol. Mater.
Eng., 2002, 287, 698.
164. N. Kawatsuki, N. Furuso, K. Goto and T. Yamamoto, J. Photopolym. Sci.
Technol., 2002, 15, 265.
165. J. Oertgren, G. Andersson, P. Busson, A. Hult, A. Eriksson and M. Lindgren,
J. Phys. Chem., 2001, 105, 10223.
166. C.L. Lester and C.A. Guymon, Polymer, 2002, 43, 3707.
167. H. Kihara, T. Miura and R. Kishi, Polymer, 2002, 43, 4523.
168. Y. He and X. Wang, Polym. Prep. (Am. Chem. Soc., Div. Polym. Chem.), 2002, 43,
453.
169. P. Sixou and C. Gautier, Polym. Adv. Technol., 2002, 13, 329.
170. C. Huang and Q.M. Zhang, Polym. Prep. (Am. Chem. Soc., Div. Polym. Chem.),
2002, 43, 1362.
274 Photochemistry, 36, 2007, 232–298
171. G. De Filpo, F.P. Nicoletta, M. Macchione, D. Cupelli and G. Chidichimo, Adv.

Funct. Mater., 2001, 11, 457.
172. I. Dierking, J. Phys D: Appl. Phys., 2002, 35, 2520.
173. D. Voloschenko, O.P. Pishnyak, S.V. Shiyanovskii and O.D. Lavrentovich, Los
Alamos National laboratory, Preprint Archive, Cond. Matter., 2001, 25th Sept.,
0109473.
174. D.J. Broer, G.N. Mol, J.A.M.M. van Haaren, J. Lub and N. Huck, Polym. Prep.
(Am. Chem. Soc., Div. Polym. Chem.), 2002, 43, 526.
175. P. Vlachos, S.M. Kelly, B. Mansoor and M. O’Neill, Chem. Commun., 2002, 874.
176. H. Wilderbeek, H. De Koning, J. Vorstenbosch, C. Chlon, K. Bastiaansen and
D.J. Kees, Jpn. J. Appl. Phys. Part I: Reg. Pap., Short Notes Rev. Pap., 2002, 41,
2218.
177. R. Jahn and T. Jung, Prog. Org. Coatings, 2001, 43, 50.
178. X.X. Liu, J.W. Huang and Y.L. Chen, Gongneng Gaofenzi Xuebao, 2001, 14, 387.
179. A. Bratus, A. Turovki, Yu. Medvedevskikh, E. Zagladko and G. Zaikov, J. Appl.
Polym. Sci., 2002, 83, 1892.
180. J.H. Lee, R.K. Prud’homme and A.I. Aksay, J. Mater. Res., 2001, 16, 3536.
181. Yu. Medvedevskikh, A. Bratus, G. Hafiychuk, A. Zaichenko, A. Kytsya,
A. Turovski and G. Zaikov, J. Appl. Polym. Sci., 2002, 86, 3556.
182. E.B. Kadossov, A.L. Kovarski, V.V. Kasparov, B.I. Zapadinski and A.P. Tikho-
nov, Polym.-Plastics Technol. Eng., 2001, 40, 767.
183. J.L. Owens, K.S. Anseth and T.W. Randolph, Macromolecules, 2002, ACS ASAP.
184. V.V. Nizhnik, L.P. Poskal and L.A. Trokhimenko, Kompozitsiini Polimerni Ma-
teriali, 2002, 23, 79.
185. A.V. Volkov, N.L. Kazanskiy and V.S. Solovjev, Int. Soc. Opt. Eng., 2002, 4680,
214.
186. V. Pamedytye, M.J.M. Abadie and R. Makuska, J. Appl. Polym. Sci., 2002, 86,
579.
187. C.S.B. Ruiz, L.D.B. Machado, J.A. Vanin and J.E. Volponi, J. Therm. Anal.
Calorim., 2002, 67, 335.
188. T. Scerzer and H. Langguth, Nucl. Instr. Meth. Phys. Res., Sect. B: Beam Int.
Mater. Atoms, 2001, 185, 276.
189. T. Scherzer, Macromol. Symp., 2002, 184, 79.
190. T. Scherzer, Vib. Spectrosc., 2002, 29, 139.
191. T. Scherzer, Appl. Spectrosc., 2002, 56, 1403.
192. M. Soldan, M. Mikula, V. Jancovicova, A. Blazkova, J. Fedak and J. Kindernay,
Petroleum Coal, 2000, 42, 152.
193. T. Lis Thomas and A.K. Mishra, Eur. Polym. J., 2002, 38, 1805.
194. (a) O. Peckan and D. Kaya, Int. J. Photoenergy, 2002, 4, 153; (b) S. Ugur,
B. Akkok and O. Peckan, Surf. Interface Anal., 2002, 33, 522.
195. M. Erdogan and O. Peckan, J. Appl. Polym. Sci., 2002, 87, 464.
196. F. Mikes, J. Baselga and S. Paz-Abuin, Eur. Polym. J., 2002, 38, 2393.
197. J. Gonzalez-Benito, F. Mikes, J. Baselga and H. Lemetyinemm, J. Appl. Polym.
Sci., 2002, 86, 2992.
198. F. Mikes, F. Gonzalez-Benito, B. Serrano, J. Bravo and J. Baselga, Polymer, 2002,
43, 4331.
199. R. Vatanparast, S. Li, K. Hakala and H. Lemmetyinen, J. Appl. Polym. Sci., 2002,
83, 1773.
200. P. Bosch, A. Fernandez-Arizpe, F. Catalina, J.L. Mateo and C. Peinado, Macro-
mol. Chem. Phys., 2002, 203, 336.
Photochemistry, 36, 2007, 232–298 275
201. M.S. Frahn, R.D. Abellon, L.H. Luthjens and J.M. Warman, Radiat. Res., Int.
Cong. Radiat. Res., 11th, Dublin, Ireland, July 18-23, 1999 (Pub. 2000), 2, 86.
202. J.L. Lenhart, J.H. Van Zanten, J.P. Dunkers and R.S. Parnas, Polym. Composites,
2002, 23, 555.
203. J.C. Quirin and J.M. Torkelson, Polymer, 2002, 44, 423.
204. Y.E. Xu and C.S.P. Sung, Macromolecules, 2002, ACS ASAP.
205. X. Zhang, Y. jin, F. Du, Z. Li and F. Li, Gaofenzi Xuebao, 2002, 5, 688.
206. M. Danko, P. Hrdlovic and E. Borsig, Polymer, 2002, 44, 389.
207. C. Peinado, A. Alonso, F.E. Salvador, J. Baselga and F. Catalina, Polymer, 2002,
43, 5355.
208. G.W. Ehrenstein, Gummi, Fasern, Kunststoffe, 2002, 55, 34.
209. K.H. Chae and H.J. Jang, J. Polym. Sci., Part A: Polym. Chem. Ed., 2002, 40,
1200.
210. J.A. Solis and B.D. Rodgers, J. Plastics Film Sheet, 2001, 17, 339.
211. J. Li, Huaxue Yanjiu Yu Yingyong, 2002, 14, 31.
212. Y. Ermolenko, T. Yoshinobu, Yu. Mourzina, K. Furuichi, H. Iwasaki, Yu. Vlasov
and M.J. Schoening, Proc. SPIE-Int. Soc. Opt. Eng., 2001, 17, 66.
213. A. Sasaki, M. Miyasaka, M. Hiro and M. Kaji, J. Photopolym. Sci. Technol., 2002,
15, 167.
214. Z.H. Zeng, X. Wang, J.W. Yang, H.Z. Wang and Y.L. Chen, Gaodeng Xuexiao
Huaxue Xuebao, 2002, 23, 1205.
215. P. Redmer, B. Jedrzejewski, M. Pietrzak, B. Paczkowska, L.A. Linden and
J. Paczkowski, Polimery, 2002, 47, 136.
216. T. Seta, Techno-Cosmos, 2002, 15, 15.
217. D.L. Starokadominskii and T.N. Solov’eva, Russ. J. Appl. Chem., 2002, 75, 138.
218. S. Guan and S. Li, Huaxue Shijie, 2001, 42, 181.
219. X. Wu, Huaxue Gongye Yu Gongcheng Jishu, 2001, 22, 1.
220. M. Shirai, Kobunshi Kako, 2001, 50, 290.
221. R. Bongiovanni, V. Lombardi, C. Nonnis, A. Priola and S. Turri, FATIPEC
Congr., 2000, 25th, 3, 187.
222. A. Merlin, M. Sylla, S. Yin, X. Allonas, M. Dossot and J.P. Fouassier, Entropie,
2001, 37, 84.
223. S. Makita, H. Kudo and T. Nishikubo, J. Photopolym. Sci. Technol., 2002, 15, 185.
224. H. Wei, H. Kou, W. Shi, K. Nie and Y. Zhan, J. Appl. Polym. Sci., 2002, 87, 168.
225. S. Zhu and W.F. Shi, Polym. Int., 2002, 51, 223.
226. Z. Feng and Y. Wang, Gongeng Cailiao, 2001, 32, 210.
227. G. Xu, H.B. Liang, W.F. Shi and J.W. Bao, Chem. Res. Chin. Univ., 2002, 18, 354.
228. H. Kou, A. Asif and W. Shi, Eur. Polym. J., 2002, 38, 1931.
229. O. Soppera, C. Croutxe-Barghorn and C. Carre, Mater. Res. Soc. Symp. Proc.,
2002, 726, 303.
230. T. Fujiwara, T. Iwata and Y. Kimura, J. Polym. Sci., Part A: Polym. Chem. Ed.,
2001, 39, 4249.
231. E. Muh, M. Steiger, J.E. Klee, H. Frey and R. Mulhaupt, J. Polym. Sci., Part A:
Polym. Chem. Ed., 2001, 39, 4274.
232. O. Soppera and B.C. Barghorn, Entropie, 2001, 37, 20.
233. D. Kuckling, C.D. Vo and S.E. Wohlrab, Langmuir, 2002, 18, 4263.
234. X. Yao, C. Pi, R. Li, Q. Wang and Q. Gao, Haxue Yanjiu, 2001, 12, 32.
235. V.A. Briskman and K.G. Kostarev, ACS Symp. Ser., 2001, 793, 97.
236. M. Aoyagi, S. Segawa, E. Jung, T. Itatani, M. Komuro and S. Matsumoto, Proc.
SPIE, 2001, 4345, 1073.
276 Photochemistry, 36, 2007, 232–298
237. B.H. Ahn, D.W. Lee and J.K. Lee, Korean Polym. J., 2001, 9, 247.
238. J. Byun, M.J. Jin and S. Choe, Kongop Hwahak, 2001, 12, 218.
239. S. Tamai, J. Kamad, T. Ono, T. Kuroki, K. Goto and A. Yamaguichi, J. Polym.
Sci., Part A: Polym. Ed., 2001, 40, 423.
240. J.P. Pillot, M. Birot, T.M. Dao, M.D. Vu, N.L.T. Hoang and T.S. Tran, Surf.
Coatings Int., Part B: Coatings Trans., 2001, 84, 197.
241. L. Abdellah, B. Boutevin, G. Caporiccio and F. Guida-Pietrasanta, Eur. Polym.
J., 2002, 38, 1515.
242. N.V. Zelentsova, S.V. Zelentsov, M.J.M. Abadie and E.N. Makaraeeva, Int.
J. Photochem. Photobiol., 2000, 3.
243. N. Yasuda, S. Yamamoto, Y. Wada and S. Yanagida, J. Polym. Sci., Part A:
Polym. Ed. Ed., 2001, 39, 4196.
244. T. Ganicz and A. Wlodzimierz, Polymery, 2001, 46, 476.
245. K. Murata, J. Sachin, H. Etori and T. Anazawa, Polymer, 2002, 43, 2845–6575.
246. L. Valette, V. Massardier, J.P. Pascault and B. Magny, J. Appl. Polym. Sci., 2002,
86, 753.
247. S. Li, Wuhan Huagong Xueyuen Xuebao, 2002, 24, 17.
248. J.W. Hong, H.K. Kim, J.A. Yu and Y.B. Kim, J. Appl. Polym. Sci., 2002, 84,
132.
249. G. Qi, H. Sun, L. Titan and S. Yang, Zhanjie, 2001, 22, 1.
250. K. Inomata and T. Nishikubo, Kanagawa Daigaku Kogaku Kenkyusho Shoho,
2001, 24, 58.
251. A. Hartwig, B. Schneider and A. Luhring, Polymer, 2002, 43, 4243.
252. C.C. Chappelow, C.S. Pinzino, M.D. Power, A.J. Holder, J.A. Morrill, L. Jeang
and J.D. Eick, J. Appl. Polym. Sci., 2002, 86, 314.
253. D. Derouet, G.T.M. Nguyen and J.C. Brosse, Eur. Polym. J., 2002, 38, 2017.
254. (a) X. Tan, A. Peng, Z. Gan and H. Xie, Gaofenzi Cailiao Kexue Yu Gongcheng,
2001, 17, 106; (b) X. Tan, A. Peng, Z. Gan and H. Xie, Chin. J. Polym. Sci., 2002,
20, 129.
255. R.M. Garipov, A.A. Efremova, S. Ju. Sofina, R.Ya. Deberdee and G.E. Zaikov,
Oxid. Commun., 2002, 25, 70.
256. H. Yuan, Z. Wang, Z. Zeng, J. Yang and Y. Chen, Reguxing Shuzhi, 2001, 16, 5.
257. J. Huang, C. Li, M. Zhang, Y. Jiang, S. Yan, Q. Huang and F. Li, Yingyong
Huaxue, 2002, 19, 10.
258. N.A. Abd El-Malak, S.H. El-Hamouly, A.Z. El-Fayoumy and E.H. El-Shamy,
Kautschuk Gummi Kunststoffe, 2001, 54, 546.
259. Y.B. Kim, H.K. Kim, J.K. Yoo and J.W. Hong, Surf. Coatings Technol., 2002
157, 40.
260. P.J. Tarcha, L. Su, T. Baker, D. Langridge, V. Shastri and R. Langer, J. Polym.
Sci., Part A: Polym. Chem. Ed., 2001, 39, 4189.
261. T. Nishikubo and A. Kameyama, Polym. Prep. (Am. Chem. Soc., Div. Polym.
Chem.), 2001, 42, 722.
262. N. Davidenko, R.G. Carrodeguas, R.S. Munoz and J.S.R. Del Barrio, Int.
J. Polym. Mater., 2002, 51, 577.
263. K. Hong, J. Kim and J. Bae, Korean Polym. J., 2001, 9, 253.
264. K. Yamada, N. Iwamoto, H. Yamane, T. Haraguichi and T. Kajiyama, J. Appl.
Polym. Sci., 2002, 86, 1272.
265. E. Andrzejewska, M.B. Bogacki and M. Andrzejeiwski, Macromol. Theor. Si-
mulat., 2002, 10, 842.
266. D.H. Choi and S.J. Oh, Eur. Polym. J., 2002, 38, 1559.
Photochemistry, 36, 2007, 232–298 277
267. O.C. Myoung, H.H. Choi, Y.S. Ku, C. Ahn, G.W. Chung and J.B. Lee, Kongop
Hwahak, 2002, 13, 131.
268. J. Chen, M.D. Soucek, W.J. Simonsick and R.W. Celikay, Polymer, 2002, 43, 5379.
269. X. Li, H. Zhou and J. Zhao, Huaxue Yanjiu, 2002, 13, 27.
270. R. Balaji and S. Nanjundan, Macromol. Rapid Commun., 2001, 22, 1186.
271. K. Subramanian, V. Krishnasamy, S. nanjundan and A.V.R. Reddy, J. Polym.
Mater., 2001, 18, 293.
272. G. Gozzelino, S. Liturri and G. Audisio, Nucl. Instr. Meth. Res., 2001, 185, 243.
273. N. Moszner, T. Volkel, S.C. Von Clausbruch, E. Geiter, N. Batliner and
V. Rheinberger, Macromol. Mater. Eng., 2002, 287, 339.
274. J.L. Mateo, M. Calvo and P. Bosch, J. Polym. Sci., Part A: Polym. Chem. Ed.,
2002, 40, 120.
275. P. Delobelle, L. Guillot, C. Dubois and L. Monney, Ann. Composites, 2001, 1, 113.
276. K. Ishizu and T. Hosokawa, Polym. Int., 2001, 50, 1186.
277. H. Kouzai, T. Makiyama and S. Shimotsuma, Kenkyu Hokoku-Kanto Gakuin
Daigaku Kogakubu, 2001, 45, 33.
278. S. Xu and W. Yang, Chem. J. Internet, 2000, 2, no pp.
279. S.Y. Kim and C.N. Choi, Polymer (Korea), 2001, 25, 642.
280. S. Islam, Nucl. Sci. Appl., 1999, 8, 87.
281. H. Yanagishita, D. Kitamoto, T. Ikegami, H. Negishi, A. Endo, k. Haraya,
T. Nakane, N. Hanai, J. Arai, H. matsuda, Y. Idemoto and N. Koura, J.
Membrane Sci., 2002, 203, 191.
282. H. Kawaguichi, Y. Isono and S. Tsuji, Macromol. Symp., 2002, 179, 75.
283. A. Maliakal, S.Y. Sung, M.J. Lee, S.K. Pearsall, N.J. Turro and M.M. Green,
Polym. Prep. (Am. Chem. Soc., Div. Polym. Chem.), 2002, 43, 1370.
284. M.A. Khan, R.A. Khan, B.S. Aliya and M.N. Islam, J. Macromol. Sci., Pure Appl.
Chem., 2002, A39, 723.
285. R. Schmidt, T. Zhao, J.B. Green and D.J. Dyer, Langmuir, 2002, 18, 1281.
286. K.H. Lee, G.J. Sun and K.H. Chae, J. Photosci., 2000, 7, 149.
287. B. Kaeselev, J. Pieracci and G. Belfort, J. Membrane Sci., 2001, 194, 245.
288. J. Liu, K. Wang, X. Liang, H. Tang, S. Xu and H. Gao, Gongneng Cailiao, 2001,
32, 534.
289. K. Matsuda, T. Nakamura, K. Yamada and M. Hirata, J. Photopolym. Sci.
Technol., 2002, 15, 335.
290. N. Sekar, Colourage, 2001, 48, 39.
291. T. Seki, Kobunshi Ronbunshu, 2002, 59, 253.
292. S. Zhu, W. Zhu and Y. Shen, Ranliao Gongye, 2001, 38, 8.
293. J. Li, Xiandai Huagong, 2001, 21, 13.
294. K. Nakajima, Kagaku, 2002, 57, 62.
295. A. Itaya, Kobunshi, 2002, 51, 85.
296. C. Devadoss, Supramol. Photosens. Electroactive Mater., 2001, 793.
297. S. Mayer and R. Zentel, Prog. Polym. Sci., 2001, 26, 1973.
298. K. Ohba, J. Photopolym. Sci. Technol., 2002, 15, 177.
299. E.M. Conwell, Springer Ser. Mater. Sci., 2001, 41, 127.
300. A.K. Singh and G.R. Mahalaxmi, Proc. Nat. Acad. Sci., India Sect. A: Phys. Sci.,
2000, 70, 1.
301. T. Yamaoka, Erekutoronikuso Jisso Gaikaishi, 2002, 5, 89.
302. S.A. Siling, E.I. Lozinskaya and Yu.E. Boressevitch, Syn. Prop. Heterocycl.
Compnd., 2001, 7.
303. S. Wang and C.S.P. Sung, Macromolecules, 2002, 35, 877.
278 Photochemistry, 36, 2007, 232–298
304. A.A.G. Shaikh and A.S. Hay, J. Polym. Sci., Part A: Polym. Ed., 2002, 40, 496.
305. G. Srinivas and B. Bagchi, J. Chem. Phys., 2002, 116, 837.
306. X. Kong, X. Liu, B. Hu and C. Jin, Faguang Xuebao, 2001, 22, 192.
307. A.H. Basta, A.S. Girgis and H. El-Saieid, Dyes Pigments, 2002, 54, 1.
308. K. Doiron, Y. Ni and A.R.P. van Heiningen, Prog. Paper Recycling, 2002, 12, 19.
309. K. Goda and H. Shimada, Res. Bull. Meisei Univ., Phys. Sci. Eng., 2002, 38, 37.
310. S. Balabanov, K. Velitchkova and K. Krezhov, Vacuum, 2002, 69, 107.
311. G. Teyssedre, G. Tardieu and C. Laurent, J. Mater. Sci., 2002, 8, 1599.
312. G. Tardieu, G. Teyssedre and C. Laurent, J. Phys. D: Appl. Phys., 2002, 35, 40.
313. M. Duran, G. Teyssedre, F. Massines and C. Laurent, Proc. IEE Int. Conf. Solid
Dielectrics, 7th, Eindhoven, June 25th, 2001, 31.
314. J.S. Uhm, R. Giesa and H.W. Schmidt, Adv. Funct. Mater., 2002, 12, 441.
315. F. Catalina, C. Peinado, N.S. Allen and T. Corrales, J. Polym. Sci., Part A: Polym.
Chem. Ed., 2002, 40, 3312.
316. T. Corrales, F. Catalina, C. Peinado, N.S. Allen and E. Fontan, J. Photochem.
Photobiol., Part A: Chem. Ed., 2002, 147, 213.
317. L. Gorghiu, S. Jipa, R. Setnescu, T. Setnescu, I. Mihalcea and T. Zaharescu, Rev.
Chim. (Bucharest), 2002, 53, 587.
318. H. Saijo, K. Kagawa and T. Tanaka, Toso Kagaku, 2001, 36, 112.
319. O.L. Kramer, E.M. Battalov, A.I. Voloshin and Yu.A. Prochukhan, Russ. J. Appl.
Chem., 2001, 74, 1190.
320. C. Peinado, N.S. Allen, E.F. Salvador, T. Corrales and F. Catalina, Polym.
Degrad. Stabil., 2002, 77, 523.
321. P. Eriksson, T. Reitberger and B. Stenberg, Polym. Degrad. Stabil., 2002, 78, 183.
322. L. Woo, C.L. Sandford and H. Blom, Ann. Technol. Conf-SPE, 60th, 2002, 2695.
323. L. Woo, C. Sandford, H. Blom and D.Y. Samuel, Thermochim. Acta, 2002, 392, 23.
324. J. Rychly, M. Strlic and L. Matisova-Rychla, Polym. Degrad. Stabil., 2002, 78, 357.
325. K.Yu. Murinov, A.I. Voloshin, N.N. Krasnogorskaya and Yu.F. Murinov, Russ.
Chem. Bull., 2002, 51, 54.
326. K.A. Alberty, E. Tillman, S. Carlotti, K. King, S.E. Bradforth, T. Hogen-Esch,
D. Parker and W.J. Feast, Macromolecules, 2002, 35, 3856.
327. R.N. Nurmukhametov, N.V. Ryzhakova, I.L. Belaits and R.R. Yunyaev, Physo-
komol. Soedin., Ser. A; Ser. B, 2001, 43, 1586.
328. F.B. Dias, J.C. Lima, A. Horta, I.F. Pierola and A.L. Macanita, Macromolecules,
2002, ACS ASAP.
329. T. Itoh and M.H. Yang, J. Polym. Sci., Part B: Polym. Phys. Ed., 2002, 40, 854.
330. S.R. Pujari, P.N. Bhosale, P.M.R. Rao and S.R. Patil, Mater. Res. Bull., 2002, 37, 439.
331. J. Pozuelo, T.D.Z. Atvars, J. Bravo and J. Baselga, Macromol. Theor. Simulat.,
2001, 10, 808.
332. U.W. Grummt, E. Birckner, M. Al-Higari, D.A.M. Egbe and E. Klemm,
J. Fluoresc., 2001, 11, 41.
333. S. Sinha, C. Rothe, A. Beeby, L.E. Horsburgh and A.P. Monkman, J. Chem.
Phys., 2002, 117, 2332.
334. S.W. Hwang and Y. Chen, Macromolecules, 2002, 35, 5438.
335. S. Kawata and H. Sun, J. Photopolym. Sci. Technol., 2002, 15, 471.
336. J. Gong, J. Yang, X. Cui, S. Wang, Z. Su and L. Qu, Synth. Met., 2002, 129, 15.
337. Y.B. Hou, L.J. Meng and M.P. Dos Santos, Acta Metallurgica Sinica, 2001, 14,
441.
338. K. Yoshida, Y. Ooyama, S. Tanikawa and S. Watanbe, J. Chem. Soc, Perkin
Trans. 2, 2002, 708.
Photochemistry, 36, 2007, 232–298 279
339. N.A. Davidenko, N.A. Derevyanko, A.A. Ishchenko, V.A. Pavlov and S.L.
Studzinskii, Theor. Exp. Chem., 2002, 37, 241.
340. C.J. Ellison and J.M. Torelson, Polym. Prep. (Am. Chem. Soc., Div. Polym.
Chem.), 2002, 43, 1345.
341. L. Latterini, F. Elisei, G.G. Aloisi, U. Costantino and M. Nocchetti, Phys. Chem.
Chem. Phys., 2002, 4, 2792.
342. K. Potje-Kamloth, B.J. Polk, M. Josowicz and J. Janata, Chem. Mater., 2002, 14,
2782.
343. J. Zhou, S. Tan, B. Zhao, Z. Xiao and X. Wang, Xiangtan Daxue Ziran Kexue
Xuebao, 2001, 74, 74.
344. G. Hungerford, E.M.S. Castanheira, M.E.C.D. Real Oliveira, M. da Gracia
Miguel and H.D. Burrows, J. Phys. Chem. B, 2002, 106, 4061.
345. E. Schab-Balcerzak, D. Sek, E. Grabiec, B. Jarzabek and Z. Mazurak, High
Perform. Polym., 2001, 13, 109.
346. Y. Fujiwara, Y. Ishikawa and Y. Amao, Nippon Kagaku Kaishi, 2002, 2, 261.
347. P. Natarajan and C. Raja, Eur. Polym. J., 2002, 37, 2207.
348. J.K. Robinson, R.R. Gustafson, J.B. Callis and C. Bruckner, TAPPI, Boston,
USA, Nov. 5-8th, 2000, 281.
349. Yu.A. Mikheev, L.N. Guseva and G.E. Zaikov, Vysokomol. Soediniya, Ser. A, Ser.
B., 2002, 44, 758.
350. Y. Amao and I. Okura, Bull. Chem. Soc. Jpn., 2002, 75, 389.
351. T. Lee, O.O. Park, J. Kim and Y.C. Kim, Macromol. Res., 2002, 10, 278.
352. E.V. Anufrieva, M.G. Krakovyak, T.D. Anan’eva, T.N. Nekrasova and R.Yu.
Smyslov, Phys. Solid State, 2002, 44, 161.
353. J.S. Parent, M.E. Scott, M.F. Cunningham and R.A. Whitney, Polym. Prep. (Am.
354. J.S. Parent, M.E. Scott, S.L. Hennigar, M.F. Cunningham and R.A. Whitney,
Macromolecules, 2002, 35, 7628.
355. A.Yu. Borisenko, V.G. Senchishin and T.V. Sakhno, Funct. Mater., 2002, 9,
343.
356. A.Yu. Borisenko and V.G. Senchishin, Mater. Res. Soc. Symp., 2002, 708, 137.
357. M.K. Park, C. Xia, R.C. Advincula, P. Schuetz and F. Caruso, Langmuir, 2001, 17,
7670.
358. A.J. Bur and S.C. Roth, Ann. Technol. Conf. SPE., 2002, 60th, Vol. 3, 3410.
359. C.J. Ellison and J.M. Torkelson, J. Polym. Sci., Part B: Polym. Phys., 2002, 40,
2745.
360. A.J. Bur, M.G. Vangel and S. Roth, Appl. Spectrosc., 2002, 56, 174.
361. J. Gonzalez-Benito, J. Bravo, F. Mikes and J. Baselga, Polymer, 2002, 44, 653.
362. M.S. Frahn, R.D. Abdellon, W.F. Jager, L.H. Luthjens and J.M. Warman, Nucl.
Instr. Meth. Phys. Res., 2001, 185, 241.
363. B.P. Wittmershaus, J.J. Skibicki, J.B. McLafferty and Yu.Z. Zhang, J. Fluoresc.,
2001, 11, 119.
364. M.E. Harmon, D. Kuckling and C.W. Curtis, Polym. Prep. (Am. Chem. Soc., Div.
Polym. Chem.), 2002, 43, 346.
365. D. Kuckling, I.G. Ivanova, H.J.P. Adler and T. Wolff, Polymer, 2002, 43, 1813.
366. K. Tsuji, M. Hayakawa, T. Onda and T. Tanaka, Trans. Mater. Res. Soc. Jpn.,
2001, 26, 639.
367. R. Jing and H. Hongfei, Eur. Polym. J., 2001, 37, 2413.
368. M. Erdogan, G. Hizal, U. Tunca, D. Hayrabetyan and O. Peckan, Polymer, 2002,
43, 1925.
280 Photochemistry, 36, 2007, 232–298
369. H.X. Li, G.C. Wang, L. Wang, Y. Wang and B. He, Gaodeng Xuexiao Huaxue
Xuebao, 2001, 22, 264.
370. J. Li, L. Wang, Y.H. Ying and Y.J. Yang, Huaxue Xuebao, 2002, 60, 1700.
371. O. Peckan and M. Erdogan, Eur. Polym. J., 2002, 38, 1105.
372. M. Erdogan, B. Yonel and O. Peckan, Polym. Int., 2002, 51, 757.
373. T. Takahashi, H. Watanabe, N. Miyagawa, S. Takahara and T. Yamaoka, Polym.
Adv. Technol., 2002, 13, 33.
374. Y. Zheng, M. Mici, S.V. Mello, M. Mabrouki, F. Andreopoulos, M. Fotios,
V. Konka, S.M. Pham and R.M. Leblanc, Macromolecules, 2002, ACS, ASAP.
375. C. Xu, H. Tamagawa, M. Uchida, S. Popovic and M. Taya, Proc. SPIE, 2001,
4329, 256.
376. O. Ikkala, M. Knaapila, M. Torkkeli, L.O. Palsson, L.E. Horsburgh, K. Jokela,
I.P. Dolbnya, W. Bras, R. Serimaa, G. ten Brinke and A.P. Monkman, Polym.
Prep. (Am. Chem. Soc., Div. Polym. Chem.), 2002, 43, 550.
377. W. de Mendes, E.H.L. Falcao and D.V. Petrov, Mol. Cryst. Liq. Cryst. Sci.,
Technol. Sect. A: Mol. Cryst. Liq. Cryst., 2002, 374, 481.
378. M. Knaapila, O. Okkala, M. Torkkeli, K. Jokela, R. Serimaa, I.P. Dolbnya,
W. Bras, G. ten Brinke, L.E. Horsburgh, L.O. Palsson and A.P. Monkman, Appl.
Phys. Lett., 2002, 81, 1489.
379. Z. Jia, Semiconductor Photonics Technol., 2001, 7, 217.
380. L. Bakueva, s. Musikhin and E.H. Sargent, J. Nanosci. Nanotechnol., 2001, 1, 457.
381. A.V. Vannikov, A.D. Grishina, L.Ya. Pereshivko, T.V. Krivenko, V.V. Savel’ev,
L.I. Kostenko and R.W. Rychwalski, High Energy Chem., 2002, 36, 38.
382. T. Uematsu, S. Maenosono, A. Watanabe and Y. Yamaguichi, J. Polym. Sci., Part
B: Polym. Phys. Ed., 2001, 40, 216.
383. M. Ariu, D.G. Lidzey, M. Sims, A.J. CAdby, P.A. Lane and D.D.C. Bradley,
J. Phys.: Condens. Matter, 2002, 14, 9975.
384. A.Yu. Borisenko, High Perform. Polym., 2001, 13, S525.
385. L. Boiteau, M. Moroni, A. Hilberer, M. Werts, B. de Boer and G. Hadziioannou,
Macromolecules, 2002, 35, 1543.
386. W.J. Joo, C.H. Oh and Y.K. Han, J. Phys. Chem. B, 2002, 106, 5378.
387. T. Ikawa, t. Shiga and A. Okada, J. Appl. Polym. Sci., 2002, 83, 2600.
388. I.L. Radtchenko, G.B. Sukhorukov, N. Gaponik, A. Kornowski, A.L. Rogach
and H. Mohwald, Adv. Mater., 2001, 13, 1684.
389. L. Zhao, K.G. Neoh and E.T. Kang, Chem. Mater., 2002, 14, 1098.
390. H. Icil, D. Uzun and E. Arslan, Spectrosc. Lett., 2001, 34, 605.
391. Y. Nishihara, R. Hidayat, A. Fujii, M. Ozaki, K. Yoshino, S.M.A. Karim and
T. Masuda, Denki Zairyo Gijitsu Zasshi, 2001, 10, 54.
392. H. Ghosh, s. Mazumdar and A. Shukla, Int. J. Mod. Phys. B, 2000, 15, 2793.
393. H. Tachibana, N. Hosaka, M. Osaki and Y. Tokura, Excitonic Proc. Condens.
Matter, Proc. Int. Conf., 4th, Osaka, Aug. 22-25th, 2000, 2001, 401.
394. S. Yamaguichi and T.m. Swager, J. Am. Chem. Soc., 2001, 123, 112087.
395. C.H. Ting, J.T. Chen and C.S. Hsu, Macromolecules, ACS ASAP.
396. T. Aida and K. Tajima, Angew. Chem., Int. Ed., 2001, 40, 3803.
397. M. Alloisio, I. Moggio, D. Comoretto, C. Cuniberti, C. Dell’Erba and
G. Dellepiane, Synth. Met., 2001, 124, 253.
398. S. Yamada, Tomakomai Kogyo Senmon Gakko Kiyo, 2001, 36, 37.
399. C.M. Cardona, T. Wilkes, W. Ong, A.E. Kaifer, T.D. McCarley, S. Pandey,
G.A. Baker, M.N. Kane, S.N. Baker and F.V. Bright, J. Phys. Chem., 2002, 106,
8649.
Photochemistry, 36, 2007, 232–298 281
400. D.F. Anghel, J.L. Toca-Herrera, F.M. Winnik, W. Rettig and R. von Klitzing,
Langmuir, 2002, 18, 5600.
401. C. Ghao, D. Yan, B. Zhang and W. Chen, Langmuir, 2002, 18, 3708.
402. M.F. Ottaviani, F.M. Winnik, S.H. Bassman and N.J. Turro, Helv. Chim. Acta,
2001, 84, 2476.
403. R. Nomura, K. Yamada and T. Masuda, Chem. Commun., 2002, 5, 478.
404. O. Shoji, D. Nakajima, M. Annake, M. Yoshikuni and T. Nakahira, Polymer,
2002, 43, 1711.
405. T.J. Tang, Yu Ye, Z.C. Chen, F.S. Du, X. Zhang and F.M. Li, Huaxue Xuebao,
2002, 60, 931.
406. T.L. Thomas, N. Sivakumar, L. Gurunathan and A.K. Mishra, Polym. Test., 2002,
22, 143.
407. S.B. Yamaki, E.A. Prado and T.D.Z. Atvars, Eur. Polym. J., 2002, 38, 1811.
408. O. Peckan and S. Ugur, Polymer, 2002, 43, 1937.
409. H. Gao, Y. Zhao, S. Fu, B. Li and M. Li, Colloid Polym. Sci., 2002, 280, 653.
410. J.J. Tulok and G.J. Blanchard, J. Phys. Chem. B., 2002, 106, 3568.
411. M. Szadkowska-Nicze and J. Mayer, Res. Chem. Intermed., 2002, 27, 823.
412. Y. Yilmar, Phys. Rev. E: Statist., Non-Linear Soft Mater. Phys., 2002, 66, 052801/1.
413. A.M. Egbe, H. Tillmann, e. Birckner and E. Klemm, Macromol. Chem. Phys.,
2001, 202, 2712.
414. T. Ahn and H.K. Shim, Macromol. Chem. Phys., 2001, 202, 3180.
415. P.K. Tsolakis, J.K. Kallitsis and A. Godt, Macromolecules, 2002, 35, 5758.
416. O. Lavastre, I. Illitchev, G. Jegou and P.H. Dixneuf, J. Am. Chem. Soc., 2002, 124,
5278.
417. K. Alimi, P. Molinie, N. Blel, J.L. Fave, J.C. Bernede and M. Ghedira, Synth.
Met., 2002, 126, 19.
418. Y. Li, G. Vamvounis and S. Holdcroft, Chem. Mater., 2002, 14, 1424.
419. J. Yang, H. Lin, M. Zheng and F. Bai, Spectrochim. Acta: Part A, 2002, 58, 593.
420. A. Verma, K. Saxena, c. Kanchan, S.K. Dhawan, R.K. Sharma, M.N. Kamala-
sanan and S. Chandra, Appl. Biochem Biotechnol., 2001, 96, 251.
421. C. Tan, M.R. Pinto and K.S. Schanze, Chem. Commun., 2002, 5, 446.
422. H. Wang, M.K. Ng and L. Yu, Polym. Prep. (Am. Chem. Soc., Div. Polym.
Chem.), 2002, 43, 518.
423. Y. Kim, D. Shin, J.H. Ahn, H.S. Kim and S.K. Kwon, Mol. Cryst. Liq. Cryst. Sci.,
424. V. Kazukauska, H. Tzeng and S.A. Chen, Mater. Sci. Forum, 2002, 384, 321.
425. S. Karabunarliev and E.R. Bittner, Almos Nat. Lab., Prep. Arch., Condens. Matter,
3rd June 2002, 0206015.
426. J. Gierschner, H.G. Mack, L. Luer and D. Oelkrug, J. Chem. Phys., 2002, 116,
8596.
427. D.A.M. Egbe, C.P. Roll, E. Birckner, U.W. Grummt, R. Stockmann and
E. Klemm, Macromolecules, 2002, 35, 3825.
428. I.K. Spiliopoulos and J.A. Mikroyannidis, J. Polym. Sci., Part A: Polym. Chem.
Ed., 2002, 40, 2591.
429. L. Liao, Y. Pang, L. Ding and F.E. Karasz, Polym. Prep. (Am. Chem. Soc., Div.
Polym. Chem.), 2002, 43, 634.
430. S.B. Park, J.S. Suh, K.W. Lee, I.H. Cho and Y.D. Park, J. Ind. Eng. Chem., 2002,
8, 46.
431. L.F. Santos, F.M. Marconi, R.F. Bianchi, A. Marletta, L.A.O. Nunes, R.M. Faria
and D.T. Balogh, Mater. Res. Soc., Symp. Proc., 2002, 708, 113.
282 Photochemistry, 36, 2007, 232–298
432. T. Sano, C.S. Tuan, R.E. Martin and A.B. Holmes, J. Photopolym. Sci. Technol.,
2002, 15, 253.
433. A. Kadaschuk, Yu. Skryshevski, Yu. Piryatinski, A. Vakhnin, E.V. Emelianova,
V.I. Arkhipov, H. Bassler and J. Shinar, J. Appl. Phys., 2002, 91, 5016.
434. H.K. Jung, C.L. Lee, J.K. Lee, J.K. Kim, S.Y. Park and J.J. Kim, Thin Solid Films,
2001, 401, 111.
435. W.Y. Wong, G.L. Lu, K.H. Choi and J.X. Shi, Macromolecules, 2002, 35, 3506.
436. E.J. Oh, J.S. Lee, J.S. Suh and I.H. Cho, Polym. J. (Tokyo), 2002, 34, 81.
437. Z. Liu, L.X. Wang, X.B. Jing and F.S. Wang, Chin. J. Polym. Sci., 2001, 19, 615.
438. E. Cloutet, C. Olivero, D. Ades, M.C. Castex and A. Siove, Polymer, 2002, 43,
3489.
439. J.W.Y. Lam, Z.L. Xie, J. Chen, Y. Dong, C.F. Qiu, H.S. Kwok and B.Z. Tang,
Polym. Mater. Sci. Eng., 2002, 86, 231.
440. K. Kim, H.R. Hong, S.W. Lee, J.I. Jin, Y. Park, B.H. Sohn, W.H. Kim and J.K.
Park, J. Mater. Chem., 2001, 11, 3023.
441. L.G. Madrigal, M. Pinto, K.S. Schanze and J.R. Reynolds, Polym. Prep. (Am.
442. P.K. Bhowmik, H. Han, J.J. Cebe and I.K. Nedeltchev, Polym. Prep. (Am. Chem.
Soc., Div. Polym. Chem.), 2002, 43, 987.
443. H. Nishihara, Asahi Garasu Zaidan Josie Kenkyu Seika Hokoku, 2001, no pp.
444. Y. Zhang, C.B. Murphy and W.E. Jones, Macromolecules, 2002, 35, 630.
445. H. Liu, S. Wang, Y. Luo, W. Tang, G. Yu, L. Li, C. Chen, Y. Luo and F. Xi,
J. Mater. Chem., 2001, 11, 3063.
446. P.K. Ng, X. Gong, S.H. Chan, L.S.M. Lam and W.K. Chan, Chem.– Eur. J., 2001,
7, 4358.
447. C. De Almeida Olivati, R.F. Bianchi, F.M. Marconi, D.T. Balogh and R. Mend-
onca Faria, Mol. Cryst. Liq. Cryst. Sci. Technol., Sect. A: Mol. Cryst. Liq. Cryst.,
2002, 374, 451.
448. K. Ueno, N. yamada, H. Tanabe and X.C.C. Li, Jpn. J. Deuterium Sci., 2001, 10, 25.
449. C. Zhan, Z. Cheng, J. Zheng, W. Zhang, Y. Xi and J. Qin, J. Appl. Polym. Sci.,
2002, 85, 2718.
450. Y.J. Pu, M. Soma, J. Kido and H. Nishide, J. Photopolym. Sci. Technol., 2002, 15,
259.
451. Y.J. Pu, M. Soma, J. Kido and H. Nishide, Chem. Mater., 2001, 13, 3817.
452. T. Mori, K. Strzelec and H. Sato, Synth. Met., 2002, 126, 165.
453. N.C. Yang, Y.H. Park and D.H. Suh, React. Funct. Polym., 2002, 51, 121.
454. A. Cravino and N.S. Sariciftci, J. Mater. Chem., 2002, 12, 1931.
455. J. Yang, H. Lin, S. Wang, Y. Li, F. bai and D. Zhu, J. Polym. Sci., Part A: Polym.
Chem. Ed., 2001, 39, 3981.
456. G. Ma, L. Guo, S. Qian, R. Wang and Y. Mo, Guangpuxue Yu Guangpu Fenxi,
2001, 21, 420.
457. M.R. Pinto and K.S. Schanze, Synthesis, 2002, 9, 1293.
458. T. Ahn, S.W. Ko, J. Lee and H.K. Shim, Macromolecules, 2002, 35, 3495.
459. D. Vyprachticky and V. Cimrova, Macromolecules, 2002, 35, 3463.
460. J. Yang, F. Bai, C. Liu, Y. Liu, P. Xie and R. Zhang, Chin. J. Polym. Sci., 2002, 20,
15.
461. D.H. Hwang and H.K. Shim, Thin Solid Films, 2002, 417, 166.
462. L. You, G. Cai, W.P. Webber and P. Lu, Polym. Prep. (Am. Chem. Soc., Div.
Polym. Chem.), 2002, 43, 623.
463. H. Detert and E. Sugiono, Synth. Met., 2002, 127, 237.
Photochemistry, 36, 2007, 232–298 283
464. Y. Shibasaki, Y. Sasada and M. Ueda, J. Photopolym. Sci. Technol., 2002, 15, 197.
465. S.E. Gradwell and C.L. Kepler, Macromolecules, 2002, 35, 2871.
466. N.S. Cho, D.H. Hwang, J.I. Lee, B.J. Jung and H.K. Shim, Macromolecules, 2002,
35, 1224.
467. S.H. Jung, D.H. Suh and H.N. Cho, Polym. Prep. (Am. Chem. Soc., Div. Polym.
Chem.), 2002, 43, 91.
468. D.J. Park, Y.Y. Noh, C.M. Chun, J. Kim and D.Y. Kim, Mol. Cryst. Liq. Cryst.
Sci., Technol. Dect A: Mol. Cryst. Liq. Cryst., 2002, 377, 73.
469. S.W. Chang, J.M. Hong, J.W. Hong and H.N. Cho, Polym. Bull., 2001, 47, 231.
470. J. Ding, M. Day, G. Robertson and J. Roovers, Macromolecules, 2002, 35, 3474.
471. A.B. Holmes, I. Rees, T. Sano, C. Fischmeister, J. Frey, U. Hennecke, C.S. Tuan,
B.S. Chuah, Y. Ma, R.E. Martin, J. Li, N. Feeder, A. Bond, F. Cacialli, S. Lim and
R. Friend, Proc. SPIE, 2002, 4464, 42.
472. J. Peng, Y. Xu, Q. Hou, Y. Niu, W. Ruan and Y. Cao, Vysokomol. Soedin., Ser. A:
Ser. B, 2002, 47, 1714.
473. D. Marsitzky, J. Murray, J.C. Scott and K.R. Carter, Chem. Mater., 2001, 13,
4285.
474. C. Im, J.M. Luton, P. Schouwink, S. Heun, H. Becker and H. Bassler, J. Chem.
Phys., 2002, 117, 1395.
475. Y. Chen and C.F. Huang, Synth. Met., 2002, 125, 379.
476. Y. Chen, Y.Y. Huang and Y. Ti, J. Polym. Sci., Part A: Polym. Chem. Ed., 2002,
40, 2927.
477. M. Zheng, L. Ding, E.E. Gurel and F.E. Karasz, J. Polym. Sci., Part A: Polym.
Chem. Ed., 2002, 40, 235.
478. S. Wang, W. Hua, X. Chen and Y. Hou, J. Appl. Polym. Sci., 2002, 85, 422.
479. M.D. Iosip, M. Bruma, J. Robison, Y. Kaminorz and B. Schultz, High Perform.
Polym., 2001, 13, 133.
480. S.J. Bai, C.C. Wu, L.W. Tu and K.H. Lee, J. Polym. Sci., Part B: Polym. Phys.
Ed., 2002, 40, 1760.
481. H. Cho and E. Kim, Macromolecules, 2002, 35, 8684.
482. Y. Aso, Y. Obara, T. Okai, S. Nishiguchi and T. Otsubo, Mol. Cryst. Liq. Cryst.
483. U. Asawapirom, R. Guntner, M. Forster, T. Farrell and U. Scherf, Synthesis, 2002,
9, 1136.
484. Z.Y. Lu, T.S. Yuan, Y.L. Chen, X.Q. Wei, W.G. Zhu and M.G. Xie, Chin. Chem.
Lett., 2002, 13, 674.
485. J. Zheng, C. Zjan, J. Qin and R. Zhan, Chem. Lett., 2002, 12, 1222.
486. L. Bukueva, D. Matheson, S. Musikhin and E.H. Sargent, Synth. Met., 2002, 126,
207.
487. D. Cho and G. Yang, Fibres Polym., 2002, 3, 60.
488. Y. Morisaki and Y. Chujo, Macromolecules, 2002, 35, 587.
489. Y. Morisaki, T. Ishida and Y. Chujo, Macromolecules, 2002, 35, 7872.
490. S. Shirai and K. Kido, Chem. Lett., 2002, 3, 386.
491. J.F. Niu, M.J. Yang and J.Z. Sun, Huaxue Xuebao, 2002, 60, 1139.
492. S. Zheng and J. Shi, Chem. Mater., 2001, 13, 4405.
493. D.A.M. Egbe, E. Birckner and E. Klemm, J. Polym. Sci., Part A: Polym. Chem.
Ed., 2002, 40, 2670.
494. D. Dini, R.E. Martin and A.B. Holmes, Adv. Funct. Mater., 2002, 12, 299.
495. R.D. Hreha, Y.D. Zhang, B. Domercq, N. Larribeau, J.N. Haddock, B. Kippelen
and S.R. Marder, Synthesis, 2002, 9, 1201.
284 Photochemistry, 36, 2007, 232–298
496. D. Sainova, A. Zen, H.G. Nothofer, U. Asawapirom, U. Scherf, R. Hagen,

T. Bieringer, S. Kostromine and D. Neher, Adv. Funct. Mater., 2002, 12, 49.
497. I.T. Kim, S.W. Lee, T.H. Kwak, J.Y. Lee, H.S. Park, S.Y. Kim, C.M. Lee,
H.E. Jung, J.G. Kang, T.J. Kim, H.J. Kang, C.M. Park and R.L. Elsenbaumer,
Polym. Int., 2002, 23, 551.
498. E. Vaganova and S. Yitzchalk, Polym. Prep. (Am. Chem. Soc., Div. Polym.
Chem.), 2002, 43, 348.
499. H. Wang, L. Duan, Y. Qiu, X. Wang and D. Liu, J. Appl. Polym. Sci., 2002, 83,
2195.
500. H. Wang, Q. Sun, Y. Li, D. Liu, X. Wang and X. Li, React. Funct. Polym., 2002,
52, 61.
501. H. Wang, X. Wang and D. Liu, Synth. Met., 2002, 126, 219.
502. I. Osaka, A. Nakamura, Y. Inoue and K. Akagi, Trans. Mater. Res. Soc. Jpn.,
2002, 27, 567.
503. J.W.Y. Lam, Y. Dong, K.K.L. Cheuk, J. Luo, Z. Xie, H.S. Kwok, Z. Mo and
B.Z. Tang, Macromolecules, 2002, 35, 1229.
504. S.J. Hart and R.D. Jiji, Analyst, 2002, 127, 1693.
505. L. Torrisi, Radiat. Phys. Chem., 2002, 63, 89.
506. A. Meyer and M. Weck, Polym. Prep. (Am. Chem. Soc., Div. Polym. Chem.), 2002,
43, 1134.
507. C. Zhang, Z. Yang and M. Ding, Gongneng Gaofenzi Xuebao, 2002, 15, 117.
508. T. Weil, E. Reuther and K. Mullen, Angew. Chem. Int. Edn., 2002, 41, 1900.
509. Y.J. Fu, T.K.S. Wong, G.M. Wang, X. Hu, S. Buddhudu, H.X. Zhang, Z.S. Gao
and M.H. Jiang, Mater. Res. Soc. Symp. Proc., 2001, 660, JJ5.9.
510. X. Zhang, D.M. Kale and S.A. Jenekhe, Macromolecules, 2002, 35, 382.
511. P.K. Bhowmik, R.A. Burchett, H. Han and J.J. Cebe, Polymer, 2002, 43, 1953.
512. S.B. Yoon and H.S. Oh, J. Korean Phys. Soc., 2002, 40, 330.
513. E.W.L. Chan, D.C. Lee, M.K. Ng, G. Wu, K.Y.C. Lee and L. Yu, J. Am. Chem.
Soc., 2002, 124, 12238.
514. S.H. Jhang, S.Y. Kim, J.H. Park, T. Ahn, D.S. Kim and Y.W. Park, AIP Conf.
Proc., 2001, 591, 489.
515. J.S. Lee, J.S. Suh and I.H. Cho, J. Ind. Eng. Chem., 2001, 7, 396.
516. M. Tamer, L. Horsburgh, A.P. Monkman, W. Brown and H.D. Burrows, Adv.
Funct. Mater., 2002, 12, 447.
517. F. Milota, A. Tortschanoff, J. Sperling, V. Szocs and H.F. Kauffmann, Trends Opt.
Photonics, 2002, 72, 358.
518. D. Hirtel, E.V. Soh, H. Bassler and L.J. Rothberg, Chem. Phys. Lett., 2002
361, 99.
519. V.R. Nikitenko, D. Hertel and H. Bassler, Chem. Phys. Lett., 2001, 348, 89.
520. H.D. Burrows, J. Sexias de Melo, C. Serpa, L.G. Arnaut, A.P. Monkman,
I. Hamblett and S. Navaratnam, J. Chem. Phys., 2001, 115, 9601.
521. J. Oguma, X. Dai and K. Akagi, Mol. Cryst. Liq. Cryst. Sci., Technol. Sect.
A: Mol. Cryst. Liq. Cryst., 2001, 365, 331.
522. X. Pan, Z. Su, R. Wang, W. Tian, J. Shen and M. Ding, Chem. Mater., 2001, 17,
129.
523. S. Tretiak, A. Saxena, R.L. Martin and A.R. Bishop, Phys. Rev. Lett., 2002, 89,
097402.
524. L. Liao and Y. Pang, J. Mater. Chem., 2001, 11, 3078.
525. Y.T. Lim, T.W. Lee, H.C. Lee and O.O. Park, Synth. Met., 2002, 128, 133.
526. Y.T. Lim, T.W. Lee, H.C. Lee and O.O. Park, Appl. Clay Sci., 2002, 21, 287.
Photochemistry, 36, 2007, 232–298 285
527. F.M. Marconi, R.F. Bianchi, R.M. Faria and D.T. Balogh, Mol. Cryst. Liq. Cryst.
528. Y. Li, G. Vamvounis and S. Holdcroft, Mater. Res. Soc. Symp. Proc., 2002, 665,
151.
529. C.J. Brabec, C. Winder, M.C. Scharber, N.S. Sariciftci, J.C. Hummelen,
M. Svensson and M. Andersson, J. Chem. Phys., 2001, 115, 7235.
530. A. Berlin, G. Zotti, S. Zecchin, G. Schiavon, M. Cocchi, D. Virgili and C. Sabatini,
J. Mater. Chem., 2002, 13, 27.
531. M.J. Caldas, E. Pettenati, G. Goldoni and E. Molinari, Appl. Phys. Lett., 2001, 79,
2505.
532. A. Cravino, Z. Antonio, H. Neugebauer, M. Maggini, S. Bucella, E. Menna,
M. Svensson, M.R. Andersson, C.J. Brabec and N.S. Sacriciftci, J. Phys. Chem. B.,
2002, 106, 70.
533. A. Cravino, G. Zerza, H. Neugebauer, M. Maggini, S. Bucella, M. Svensson,
M.R. Andersson, C.J. Brabec and N.S. Sacriciftci, Proc. Electrochem. Soc., 2001, 11, 94.
534. K. Tada and M. Onoda, Denki Zairyo Gijutsu Zasshi, 2001, 10, 49.
535. C. Rothe, S. Hintschich, A.P. Monkman, M. Svensson and M.R. Anderson,
J. Chem. Phys., 2002, 116, 10503.
536. L. Angiolini, E. Salatelli, A. Bolognesi and C. Botto, e-Polymers, 2002, 41, 190902.
537. S. Kim, T. Ahn, S. Han, E.R. Kim and H. Lee, Mol. Cryst. Liq. Cryst. Sci.,
538. J.M. de Souza, P.N.M. dos Anjos, E.C. Pereira, Y.G. Gobato and L.S. dos Santos,
Synth. Met., 2002, 130, 121.
539. J.D. Tovar, A. Rose and T.M. Swager, J. Am. Chem. Soc., 2002, 124, 7762.
540. R.L. Pilston and R.D. McCullough, Polym. Mater. Sci. Eng., 2002, 86, 191.
541. M. Miyasaka, T. Yamazaki and H. Nishide, Polymer J., 2002, 33, 849.
542. M. Nakamura, M. Tabata, T. Sone, Y. Mawatari and A. Miyasaka, Macromol-
ecules, 2002, 35, 2000.
543. N. Kurokawa, H. Yoshikawa, H. Masuhara, N. Hirota and K. Hyodo, J. Phys.
Chem. B., 2002 ACS ASAP.
544. G. Jegou and S. A. Jenekhe, Macromolecules, 2002, 34, 7926.
545. F. Meinardi, M. Cerminara, A. Sasella, A. Borghesi, P. Spearman, G. Bongiovanni,
A. Mura and R. Tubino, Phys. Rev. Lett., 2002, 89, 157403.
546. C. Bertarelli, M.C. Gallazzi, F. Stellacci, G. Zerbi, S. Stagira, M. Nisoli and S. de
Silvestri, Chem. Phys. Lett., 2002, 359, 278.
547. K. Inouchi, S. Kobashi, K. Takimiya, Y. Aso and T. Otsubo, Org. Lett., 2002, 4,
2533.
548. F. Brustolin, F. Goldoni, E.W. Meijer and N.A.J.M. Sommerdijk, Macromole-
cules, 2002, 35, 1054.
549. D. Hertel, H. Bassler, R. Guenter and U. Scherf, J. Chem. Phys., 2001, 115, 10007.
550. K.A. Coplin, A.L. Habakuk and D.T. Glatzhofer, Synth. Met., 2001, 124, 271.
551. A.J. Cadby, C. Yang, S. Holdcroft, D.D.c. Donal and P.A. Lane, Adv. Mater.,
2002, 14, 57.
552. Z. Liu, Q. Fang, Y. Wang, G. Xue, W. yu, Z. Shao and M. Jiang, Chem. Commun.,
2002, 2900.
553. E.N. Bodunov, M.N. Berberan-Santos and J.M.G. Martinho, Opt. Spectrosc.,
2001, 91, 873.
554. K. Chen, X. Sun and L.H. Tang, Phys. Lett. A., 2002, 294, 113.
555. E.N. Bodunov, M.N. Berberan-Santos and J.M.G. Martinho, Chem. Phys., 2001,
274, 243.
286 Photochemistry, 36, 2007, 232–298
556. Y. Qiu, Y. Yang, Q. yang, C. Wang, G. Sun, Z. Wei and H. Fei, Gangzi Xuebao,
2001, 30, 1102.
557. G. Srinivas, K.L. Sebastian and B. Bagchi, J. Chem. Phys., 2002, 116, 7276.
558. S.A. Siling, S.V. Shamahin, I.A. Ronova, A.Ya. Kovaleski, A.B. Grachev, I.Yu.
Tsiganova and V.I. Yuzhakov, Synth. Prop. Heterocycl. Cmpnd., Nova Science
Pub., N.Y., 2001, 69.
559. T. Nagai, M. Shimada and T. Nishikubo, Chem. Lett., 2001, 12, 1308.
560. Y. Matsui, S. Seki and S. Tagawa, Chem. Phys. Lett., 2002, 357, 346.
561. H. Wang, Y. Jiang, Q. Li, X. Zhang and S. Wu, Gaofenzi Xuebao, 2001, 6, 706.
562. D. Bogdal, V. Yashchuk, J. Pielichowski, T. Ogul’chansky, M. Warzala and
V. Kudrya, J. Appl. Polym. Sci., 2002, 84, 1650.
563. G. Ma, L. Guo, J. Mi, S. Qian, W. She, Z. Cai and J. Zhou, Guangpuxue Yu
Guangpu Fenxi, 2002, 22, 92.
564. S.E. Miller, Y. Zhao, R. Schaller, V. Mulloni, E.M. Just, R.C. Johnson and
M.R. Wasielewski, Chem. Phys., 2002, 275, 167.
565. X. Yuan, Z. Chen and J. Chai, Guangpuxue Yu Guangpu Fenxi, 2002, 22, 198.
566. A. Rose, C.G. Lugmair and T.M. Swager, J. Am. Chem. Soc., 2001, 123, 11298.
567. Y. Chen, C.K. Liao and T. Wu, Polymer, 2002, 43, 4545.
568. M. Ohoka, J. Kuno, K. Yamashita, H. Ohkita, S. Ito, Y. Tsuji and T. Fukuda,
569. X. Feng and C. Pan, ChemPhysChem, 2002, 3, 539.
570. K. Bronk and S. Thayumanavan, Polym. Mater. Sci. Eng., 2002, 86, 50.
571. M. Alvaro, B. Ferrer and H. Garcia, Chem. Phys. Lett., 2002, 351, 374.
572. M. Xu, K. Tan, T. Zhang and X.H. Yu, Gongneng Gaofenzi Xuebao, 2001, 14,
481.
573. T. Aida and D. Jiang, Mirai Zairyo, 2001, 1, 38.
574. V. Rozhkov, D. Wilson and S. Vinogradov, Macromolecules, 2002, 35, 1991.
575. S. Machida, K. Sugihara, I. Takahashi, K. Horie, D.L. Jiang and T. Aida,
J. Polym. Sci., Part A: Polym. Phys. Ed., 2002, 40, 210.
576. Q. He, T. Lin and F. Bai, Chin. Sci. Bull., 2001, 46, 636.
577. M. Nakazono, L. Ma and K. Zaitsu, Tetrahedron Lett., 2002, 43, 8185.
578. R. Gronheid, J. Hofkens, F. Koehn, T. Weil, E. Reuther, K. Muellen and
F.C. DeSchryver, J. Am. Chem. Soc., 2002, 124, 2418.
579. A. Herrmann, T. Weil, V. Sinigersky, U.W. Wiesler, T. Vosch, J. Hofkens,
F.C. De Schryver and K. Mullen, Chem.– Eur. J., 2001, 7, 4844.
580. S. Wang and R.C. Advincula, Org. Lett., 2001, 3, 3831.
581. L.X. Liao, D.M. Junge and D.V. McGrath, Macromolecules, 2002, 35, 319.
582. F. Voegtle, M. Gorka, R. Hesse, P. Ceroni, M. Maestri and V. Balzani, Photochem.
Photobiol. Sci., 2002, 1, 45.
583. R.M. Sebastian, J.C. Blais, A.M. Caminade and J.P. Majoral, Chem.– Eur. Polym.
J., 2002, 8, 2172.
584. K. Ishizu, Y. Ohta and S. Kawauchi, Macromolecules, 2002, 35, 3781.
585. H.A. Klok, S. Becker, F. Schuh, T. Pakula and K. Mullen, Mol. Chem. Phys.,
2002, 203, 1106.
586. C. Gao, D. Yan and W. Chen, Macromol. Rapid Commun., 2002, 23, 465.
587. K. Xu, H. Peng, Q. Sun, Y. Dong, F. Salhi, J. Luo, J. Chen, Y. Huang, D. Zhang,
Z. Xu and B.Z. Tang, Macromolecules, 2002, 35, 5821.
588. S.C.J. Meskers, M. Bender, J. Huebner, Yu.V. Romanovskii, M. Oestreich,
A.P.H.J. Albertus, E.W. Meijer and H. Baessler, J. Phys. Chem., 2001, 105, 10220.
589. C.C. Kwok and M.S. Wong, Chem. Mater., 2002, 14, 3158.
Photochemistry, 36, 2007, 232–298 287
590. A. Dirksen, E. Zuidema, R.M. Williams, L. De Cola, C. Kauffmann, F. Voegtle,

A. Roquw and F. Pina, Macromolecules, 2002, 35, 2743.
591. D.L. Richter, A. Tesfai and S.A. Tucker, Anal. Chem., 2001, 73, 5743.
592. A.K. Holley, D. He, R. Morgan and M. Chai, Polym. Prep. (Am. Chem. Soc., Div.
Polym. Chem.), 2002, 43, 382.
593. S. Kim, D.W. Chang, s.Y. Park, H. Kawai and T. Nagamura, Macromolecules,
2002, 35, 2748.
594. S.H. Battah, C.E. Chee, H. Nakanishi, S. Gerscher, A.J. MacRobert and
C. Edwards, Bioconjugate Chem., 2001, 12, 980.
595. L. Ma, S.J. Lee and W. Lin, Macromolecules, 2002, 35, 6178.
596. M. Ryner, A. Valdre and A.C. Albertsson, J. Polym. Sci., Part A: Polym. Chem.
Ed., 2002, 40, 2049.
597. J.J. Kim, K.S. Kim, S. Baek, H.C. Kim and M. Ree, J. Polym. Sci., Part A: Polym.
Chem. Ed., 2002, 40, 1173.
598. N.C. Yang, H.W. Choi and D.H. Suh, Polym. Mater. Sci. Eng., 2002, 86, 255.
599. S.W. Hwang, S.H. Chen and Y. Chen, J. Polym. Sci., Part A: Polym. Chem. Ed.,
2002, 40, 2215.
600. P.J. Costanzo and K. Kristoffer, Macromolecules, 2002, 35, 6804.
601. J. Gonzalez-Benito, A. Aznar and J. Baselga, J. Fluoresc., 2001, 11, 307.
602. (a) K. Wang, W. Huang, P. Xai, C. Gao and D. Yan, Ganguang Kexue Yu Guang
Huaxue, 2002, 20, 161; (b) K. Wang, W. Huang, P. Xai, C. Gao and D. Yan,
Gaofenzi Xuebao, 2002, 3, 385.
603. K. Wang, W. Huang, P. Xai, C. Gao and D. Yan, React. Funct. Polym., 2002, 52, 143.
604. H. Tanaka, A. Swergin, L. Odberg and M. Tanaka, J. Appl. Polym. Sci., 2002, 86,
672.
605. G.L. Gao, Yu. Fang, X.H. Zhu, D.D. Hu, S.X. Liu and Y.L. Cui, Gaodeng
Xuexiao Huaxue Xuebao, 2002, 23, 2177.
606. S.A. Siling, E.I. Lozinskaya and Ju.E. Borisevich, Synth. Prop. Heterocycl.
Cmpnd., (Nova Science Publishers, N.Y.), 2001, 51.
607. T. Mutai, J.D. Cheon, G. Tsuchiya and K. Araki, J. Chem. Soc., Perkin Trans. 2,
2002, 5, 862.
608. P. Kujawa, R.C.W. Liu and F.M. Winnik, J. Phys. Chem. B., 2002, 106, 5578.
609. S. Morita, F. Tsunomori and H. Ushiki, Eur. Polym. J., 2002, 38, 1863.
610. C.L. Chochos, G. kandilioti, V.A. Deimede and V.G. Gregoriou, J. Macromol.
Sci., Pure Appl. Chem., 2002, 39, 1317.
611. L. Lu, R.M. Jones, R. Helgeson, D. McBranch and D. Whitten, Polym. Mater. Sci.
Eng., 2002, 86, 17.
612. C. Carbonneau, R. Frantz, J.O. Durand, M. Granier, G.F. Lanneau and
R.J.P. Corriu, New J. Chem., 2001, 25, 1398.
613. L.F. Campo, d.S. Correa and V. Stefani, Mol. Cryst. Liq. Cryst. Sci., Technol. Sect.
A: Mol. Cryst. Liq. Cryst., 2002, 374, 373.
614. H. Augier, G. Clavier, F. Ilhan, G. Cooke and V. M. Rotello, Chem. Commun.,
2001, 2232.
615. S. Inaoka and R. Advincula, Macromolecules, 2002, 35, 2426.
616. M. Wang, K. Liu, G. Gao and Yu. Fang, Shaanxi Shifan Daxue Xuebao Ziran
Kexueban, 2002, 30, 78.
617. C.J. Ellison, S.D. Kim, D.B. Hall and J.M. Torkelson, Eur. Phys. J., E: Soft
Matter, 2002, 8, 155.
618. A. Bajorek, M. Ciepluch and J. Paczkowski, J. Polym. Sci., Part A: Polym. Chem.
Ed., 2002, 40, 3481.
288 Photochemistry, 36, 2007, 232–298
619. H. Sawada, Y. Inui, T. Kawase, M. Baba and T. Tomita, Mater. Technol., 2001,
19, 44.
620. Y.S. Gal, W.C. Lee, J.W. Park, B.S. Kim, S.H. Jang and S.H. Jin, Mol. Cryst. Liq.
Cryst. Sci., Technol. Sect. A: Mol. Cryst. Liq. Cryst., 2001, 371, 289.
621. V. Goertz and H. Ritter, Macromolecules, 2002, 35, 4258.
622. G.V. Zakharova and A.K. Chibisov, High Energy Chem., 2001, 35, 417.
623. I. Grabchev, V. Bojinov and C. Petkov, Dyes Pigments, 2001, 51, 1.
624. R.D. Falcone, N.M. Correa, M.A. Biasutti and J.J. Silber, Langmuir, 2002, 18,
2039.
625. A.H. Ackerman and R.J. Hurtubise, Appl. Spectrosc., 2002, 56, 1368.
626. A. Priev, S. Zalip, R. Cohen and Y. Barenholz, Langmuir, 2002, 18, 617.
627. S. Kawaguchi, M. Maniruzzaman, K. Katsuragi, H. Matsumoto, K. Ito,
N. Hugenberg and M. Schmidt, Polym. J., 2002, 34, 253.
628. C. Wang, Z. Tong, F. Zheng, B. Ren and X. Liu, Colloid Polym. Sci., 2002, 280,
814.
629. A. Toyotama, J. Yamanaka and M. Yonese, Colloid Polym. Sci., 2002, 280, 539.
630. H.S. Kang, S.R. Yang, J.D. Kim, S.H. Han and I. Chang, Polym. J., 1999, 31,
1079.
631. P. Sehgal, H. Doe and M.S. Bakshi, J. Surf. Deterg., 2002, 5, 123.
632. Y.J. An, Environ. Prog., 2001, 20, 240.
633. N. Baden, O. Kajimoto and K. Hara, J. Phys. Chem., 2002, 106, 8621.
634. M. Stork, B.S. Gaylord, A.J. Heeger and G.C. Bazan, Adv. Mater., 2002, 14, 361.
635. Y. Itoh and H. Shirai, Polym. Adv. Technol., 2002, 13, 40.
636. K. Ishizu and Y. Ohta, J. Mater. Sci. Lett., 2000, 41, 1405.
637. A. Safavi and M.A. Karimi, Anal. Chim. Acta, 2002, 468, 53.
638. S. De, A. Girigoswami and S. Mandal, Spectrosc. Acta: Part A: Mol. Biomol.
Spectrosc., 2002, 58A, 2547.
639. Y. Chang, R. Prange, H.R. Allcock, S.C. Lee and C. Kim, Macromolecules, 2002,
35, 8556.
640. Z. Li, G. Liu, S.J. Law and T. Sells, Biomacromolecules, 2002, 3, 984.
641. S. Kanagalingham, J. Spartalis, T. Cao and J. Duhamel, Polym. Prep. (Am. Chem.
642. S. Jeon, S. Granick, K.W. Kwon and K. Char, Macromolecules, 2002, 40, 2883.
643. M. Valero, A. Del Arco-Gomez and L. Rodriguez, J. Inclusion Phenom. Macro-
cycl. Chem., 2002, 42, 121.
644. Y. Fu, H. Chen, D. Qiu, Z. Wang and X. Zhang, Langmuir, 2002, 18, 4989.
645. L.I.W. Mikrajuddin, K. Okuyama and F.G. Shi, J. Electrochem. Soc., 2002, 149,
107.
646. J.W. Kim, J.S. Kim, H.R. Oh and J.A. Yu, Polym. Prep. (Am. Chem. Soc., Div.
Polym. Chem.), 2002, 43, 419.
647. R. Dondon, F. Bertorelle and S. Fery-Forgues, J. Fluoresc., 2002, 12, 163.
648. S. Jeon, S.C. Bae, J. Turner and S. Granick, Polymer, 2002, 43, 4651.
649. S. Picarra, E.J.N. Pereira, E.N. Bodunov and J.M.G. Martinho, Macromolecules,
2002 ACS ASAP.
650. Z.H. Xie, X.C. Lin and G.N. Chen, Anal. Sci., 2001, 17, 61.
651. M. Lin, W. Zhang and W. Weng, Zhongguo Xitu Xuebao, 2002, 20, 107.
652. J. Dai, A.M. Balachandra, J.I. Lee and M.L. Bruening, Macromolecules, 2002, 35,
3164.
653. L. Liu, X. Zhang and L. Zhang, Hecheng Xiangjiao Gongye, 2002, 25, 112.
654. P. Liu, D. Liang, Z. Tong and X. Liu, Macromolecules, 2002, 35, 1487.
Photochemistry, 36, 2007, 232–298 289
655. M.V. Petukhova, N.V. Petrochenkova, A.G. Mirochnik, V.E. Karasev and
E.F. Radaev, Vysokomol. Soedin., Ser. A, Ser. B, 2002, 44, 1267.
656. M. Wang, X. Li, Y. Ning and G. Cai, Beijing Shifan Daxue Xuebao Ziran
Kexueban, 2002, 38, 96.
657. Y. Guo, Y. Yang, C. Guo, E. Wang, Y. Zou and S. Feng, J. Mater. Chem., 2002,
12, 3046.
658. J.L. Bender, P.S. Corbin, C.L. Fraser, D.H. Metcalf, F.S. Richardson,
E.L. Thomas and A.M. Urbas, J. Am. Chem. Soc., 2002, 124, 8526.
659. G. Montavon, S. Markai, I. Billard, A. Nehlig and B. Grambow, Radiochim. Acta,
2002, 90, 289.
660. D.F. Parra, H.F. Brito, J. Do Rosario Matos and L.C. Dias, J. Appl. Polym. Sci.,
2002, 83, 2716.
661. A.J. Lees, Mol. Supramol. Photochem., 2001, 7, 209.
662. N.V. Petrochenkova, B.V. Bukvetskii, A.G. Mirochnik and V.E. Karasev, Russ. J.
Coord. Chem., 2002, 28, 64.
663. J.Y. Tang, M.J. Mei and W.G. Zhang, Huaxue Xuebao, 2001, 59, 2202.
664. E. Holder, D. Oelkrug, H.J. Egelhaaf, H.A. Mayer and E. Linner, J. Fluoresc.,
2002, 12, 383.
665. Y.S. Cho, C.S. Ihn, H.K. Lee and J.S. Lee, Macromol. Rapid Commun., 2001, 22,
1249.
666. W.K. Chan, S. Hou and K.Y. Man, Polym. Prep. (Am. Chem. Soc., Div. Polym.
Chem.), 2002, 43, 343.
667. H. Tong, J. Lixiang and F. Wang, Macromolecules, 2002, 35, 7169.
668. C.P. Wu, J. Liu, D. Huang, T.Q. Liu, X.X. Yu and A.H. Zhao, Gaofenzi Cailiao
Kexue Yu Gongcheng, 2002, 18, 174.
669. S.A. Siling, S.V. Shamshin, A.V. Grabchev, O.Yu. Tsiganova, V.I. Yuzhakov,
I.G. Abramov, A.V. Smirnov, S.A. Ivanovskii, A.G. Vitukhovskii, A.S. Averyushkin
and B.C. Lap, Synth. Prop. Heterocycl. Cmpnd., Nova Science, N.Y., 2001, 93.
670. I.A. Ronova, A.Yu. Kovalesky, S.V. Shamshin, A.B. Grabchev and I.Yu. Tsiga-
nova, Synth. Prop. Heterocycl. Cmpnd., Nova Science, N.Y., 2001, 37.
671. O. Maury, J.P. Guegan, T. Renouard, A. Hilton, P. Dupau, N. Sandon, L. Toupet
and H. Le Bozec, New J. Chem., 2001, 25, 1553.
672. J. Tang, L. Xiao and W. Zhang, Huaxue Xuebao, 2002, 60, 1490.
673. M.J. Tapia and H.D. Burrows, Langmuir, 2002, 18, 1872.
674. B.J. Gao, Y.F. Yang, Y. Cheng and D.J. Shi, Guangpuxue Yu Guangpu Fenxi,
2002, 22, 371.
675. M. Suzuki, M. Kimura, K. Hanabusa and H.H. Shirai, Proc. SPIE-Int. Soc. Opt.
Eng., 2001, 202, 3506.
676. H. Yu, H. Jiang, Y. Lian, X. Wang and D. Liu, Polym. Prep. (Am. Chem. Soc.,
Div. Polym. Chem.), 2002, 43, 601.
677. C.D. Colson, C.L. Lester and C.A. Guymon, Mater. Res. Soc. Symp., 2002, 709,
285.
678. C.L. Lester, S.M. Smith and C.A. Guymon, Macromolecules, 2001, 34, 8587.
679. A.T. Ionescu, E.S. Barna, G. Barbero and A.L. Alexe-Ionescu, Phys. Rev. E: Stat,
Nonlinear Soft Matter Phys., 2002, 65, 041710/1.
680. A. Arcioni, R. Tarroni and C. Zannoni, Chem. Phys. Lett., 2002, 365, 8.
681. S. Arisi, P. Camorani, L. Cristofolini, M.P. Fontanna and M. Laus, Mol. Cryst.
Liq. Cryst. Sci., Technol. Sect. A: Mol. Cryst. Liq. Cryst., 2001, 372, 241.
682. P. Sixou, C. Gautier and H. Guillard, Mol. Cryst. Liq. Cryst. Sci., Technol. Sect. A:
Mol. Cryst. Liq. Cryst., 2001, 364, 665.
290 Photochemistry, 36, 2007, 232–298
683. T. Mihara, M. Tsutsumi and N. Koide, Polym. J., 2002, 34, 347.
684. D.H. Choi and Y.K. Cha, Polym. Bull., 2002, 48, 48.
685. W.J. Lee, J.C. Li, S.H. Paek, K. Song and J.Y. Chang, Korean Polym. J., 2001, 9,
339.
686. Y. Nakamoto, K. Yonetake and J. Kido, Polym. J., 2002, 34, 601.
687. M. Sato, Y. Nakamoto and N. Tanino, Polym. J., 2002, 34, 158.
688. K.L. Sandhya, P.S. Krishna and G.G. Nair, Phys. Rev. E: Stat. Nonlinear Soft
Matter Phys., 2000, 64, 041702/1.
689. A. Sautter, C. Thalacker and F. Wuerhner, Angew. Chem., Int. Edn., 2001, 40,
4425.
690. G. Fan, S. Chung, L. Wu, Y. Wu and C. Hsu, Polym. Prep. (Am. Chem. Soc., Div.
Polym. Chem.), 2002, 43, 668.
691. P.K. Bhowmik, H. Han, J.J. Cebe, R.A. Burchett and A.A. Sarker, J. Polym. Sci.,
Part A: Polym. Chem., 2002, 40, 659.
692. P.K. Bhowmik, H. Han, J.J. Cebe and R.A. Burchett, J. Polym. Sci., Part A:
Polym. Chem. Ed., 2001, 40, 141.
693. R. Rosenhauer, Th. Fishcer, S. Czapla, J. Stumpe, A. Vinuales, M. Pinol and J.L.
Serrano, Mol. Cryst. Liq. Cryst. Sci., Technol. Sect. A: Mol. Cryst. Liq. Cryst.,
2001, 364, 295.
694. Z. Zhu and T.M. Swager, J. Am. Chem. Soc., 2002, 124, 9670.
695. S. Yoneyama, T. Yamamoto, M. Hasegawa, O. Tsutsumi, A. Kanazawa,
T. Shiono and T. Ikeda, J. Mater. Chem., 2001, 11, 3008.
696. M. Han, G. Galli, L. Komitov, K. Ichimura and E. Chiellini, Mol. Cryst. Liq.
Cryst. Sci., Technol. Sect. A: Mol. Cryst. Liq. Cryst., 2001, 365, 459.
697. F. Roussel, c. Delorrier, U. Maschke and J. Buisine, Mol. Cryst. Liq. Cryst. Sci.,
698. F.P. Nicoletta, G. De Filpo, D. Cupelli, M. Macchione and G. Chidichimo, Appl.
Phys. Lett., 2001, 79, 4325.
699. J.W.Y. Lam, Y.L.J. Dong, K.K.L. Cheuk, Z. Xie and B.Z. Tang, Thin Solid Film.,
2002, 417, 143.
700. M. Xu, Hubei Huagong, 2002, 19, 21.
701. V.P. Shibaev, A.Yu. Bobrovsky and N.I. Natalia, Mater. Res. Soc. Symp. Proc.,
2002, 709, 79.
702. B. Chen, M. Wang, Y. Wu and H. Tian, Chem. Commun., 2002, 10, 1060.
703. S. Shim and T. Joo, Trends Opt. Photonics, 2002, 72, 363.
704. C.D. Gabutt, T. Gelbrich, J.D. Hepworth, B.M. Heron, M.B. Hursthouse and
S.M. Partington, Dyes Pigments, 2002, 54, 79.
705. M.M. Krayushkin, V.Z. Shirinian, L.I. Belen’kii, A.Yu. Shadronov, A.Yu.
MArtynkin and B.M. Uzhinov, Mendeleev Commun., 2002, 4, 141.
706. M.V. Kozlovsky, W. Haase and M. Rehahn, Mater. Res. Soc. Symp. Proc., 2002,
709, 15.
707. A. Natansohon and P. Rochon, Chem. Rev., 2002, 102, 4139.
708. S.N. Zhao, J.P. Zhuang, Y. Zen and W.Q. Zhang, Gaodeng Xuexiao Huaxue
Xuebao, 2001, 22, 256.
709. S. Ghosh and A.K. Banthia, J. Polym. Sci., Part A: Polym. Chem. Ed., 2001, 106,
4182.
710. I. Zebger, M. Rutloh, U. Hoffmann, J. Stumpe, H.W. Siesler and S. Hvilsted, J.
Phys. Chem. A., 2002, 106, 3454.
711. S.H. Kang, H.D. Shin, C.H. Oh, D.H. Choi and K.H. Park, Bull. Korean Chem.
Soc., 2002, 203, 957.
Photochemistry, 36, 2007, 232–298 291
712. P.J. Coelho, L.M. Carvalho, S. Rodrigues, A.M.F. Oliveira-Campos, R. Dubest,

J. Aubard, A. Samat and R. Guglielmetti, Tetrahedron, 2002, 58, 925.
713. W. Liu, S.H. Lee, S. Yang, S. Bian, L. Li, L.A. Samuelson, J. Kumar and
S.K. Tripathy, J. Macromol. Sci., Pure Appl. Chem., 2001, A38, 1355.
714. K. Kago, T. Seki, R.R. Schuecke, E. Mouri, H. Matsuoka and H. Yamaoka,
Langmuir, 2002, 18, 3875.
715. T. Hayakawa, S. Horiuchi, H. Shimizu, T. Kawaazoe and M. Ohtsu, J. Polym.
Sci., Part A: Polym. Chem. Ed., 2002, 40, 2406.
716. D.R. Robello, S. Farid, J. Dinnocenzo and J.G. Gillmore, Polym. Prep. (Am.
717. U. Gubler, D. Wright, W.E. Moerner and M.B. Klein, Opt. Lett., 2002, 27, 354.
718. H. Ikake, Y. Fukuda, S. Shimizu, K. Kurita and S. Yano, Kobunshi Ronbunshu,
2002, 59, 608.
719. T. Ikehara, M. Tanaka, S. Shimada and H. Matsuda, Proc. SPIE, 2001, 4234,
215.
720. F. Dietz and N. Tyutyulkov, Phys. Chem. Chem. Phys., 2001, 3, 4600.
721. G.D. Jaycox, Polymer J. (Tokyo), 2002, 34, 280.
722. T. Buruiana and E.C. Buruiana, J. Appl. Polym. Sci., 2002, 86, 1240.
723. F. Lin and F.W. Harris, Polym. Prep. (Am. Chem. Soc., Div. Polym. Chem.), 2002,
43, 57.
724. K. Huang and M. Wan, Chem. Mater., 2002, 14, 3486.
725. K. Huang and M. Wan, Macromolecules, 2002, 35, 8653.
726. M. Hasegawa, T. Ikawa, M. Tsuchimori and O. Watanabe, J. Appl. Polym. Sci.,
2002, 86, 17.
727. Y. Wu, A. Natanshon and P. Rochon, Macromolecules, 2001, 34, 7822.
728. Y. He, X. Wang and Q. Zhou, Gaofenzi Xuebao, 2002, 3, 336.
729. L.S. Kol’tsova, N.L. Zaichenko, A.I. Shivonok and V.S. Maratsev, Russ. Chem.
Bull., 2001, 50, 1214.
730. R. Nakao, F. Noda, A. Toyokazu and Y. Abe, Polym. Adv. Technol., 2002, 13, 81.
731. S.H. Kim, H.J. Suh, J.Z. Cui, Y.S. Gal, S.H. Jin and K.N. Koh, Dyes Pigments,
2002, 53, 702.
732. R. Nakao, T. Horii, Y. Kushino, K. Shimaoka and Y. Abe, Dyes Pigments, 2002,
52, 95.
733. F. Maurel, J. Aubard, M. Rajzmann, R. Guglielmetti and A. Samat, J. Chem. Soc.,
Perkin Trans 2, 2002, 1307.
734. E. Volker, M. O’Connell, M.R. Negri and P.F. Aramendia, Helv. Chim. Acta,
2001, 84, 2751.
735. E.B. Barmatov, A.V. Medvedev, S.A. Ivanov and V. Shibaev, Vysokomol. Soedin.
Ser. A, Ser. B., 2002, 44, 61.
736. M. Sato and T. Yamashita, J. Photopolym. Sci. Technol., 2002, 15, 115.
737. E. Ortyl, R. Janik and S. Kucharski, Eur. Polym. J., 2002, 38, 1871.
738. B.M. Schultz, M.R. Huber, T. Bieringer, G. Kraudch and S.J. Zilker, Synth. Met.,
2001, 124, 155.
739. X. Hu, X. Zhao, L.H. Gan and X. Xia, J. Appl. Polym. Sci., 2002, 83, 1061.
740. M.Y. Jeong, J.W. Wu and J.I. Jin, Mol. Cryst. Liqu. Cryst. Sci., & Technol. Sect.
A: Mol. Cryst. And Liqu. Cryst., 2001, 371, 253.
741. Y. Deng, X. Tuo, H. Cheng and X. Wang, Polym. Prep. (Am. Chem. Soc., Div.
Polym. Chem.), 2002, 43, 9.
742. X. Liu, X. Wang and D. Liu, Polym. Prep. (Am. Chem. Soc., Div. Plym. Chem.),
2002, 43, 688.
292 Photochemistry, 36, 2007, 232–298
743. A. Zeigler, J. Stumpe, A. Toutianoush and B. Tieke, Colloids Surf., A: Physico-

chem. Eng. Aspects, 2002, 198, 777.
744. L. Wu, H. Peng, X. Wang, D. Liu and Q. Zhou, Tsinghua Sci. Technol., 2001, 6,
173.
745. I. Suzuki, T. Ishizaki, T. Hoshi and J. Anzai, Macromolecules, 2002, 35, 577.
746. A.E. Ivanov, N.L. Eremeev, P.O. Wahlund, I.Yu. Galaev and B. Mattiasson,
Polymer, 2002, 43, 3819.
747. T. Deligeorgiev, S. Minkovska, B. Jejiazkova and S. Rakovsky, Dyes Pigments,
2002, 53, 101.
748. K. Fukuda, T. Seki and K. Ichimura, Trans. Mater. Res. Soc. Jpn., 2001, 26, 901.
749. L. Komitov, B. Helgee, G. Andersson and T. Hjertberg, Macromol. Chem. Phys.,
2002, 203, 1724.
750. K. Fukuda, T. Seki and K. Ichimura, Macromolecules, 2002, 35, 1951.
751. J. Zhi, B. Zhang, B. Baoyan and G. Shi, J. Appl. Polym. Sci., 2002, 85, 2155.
752. O.A. Fedorova, Y.P. Strokach, S.P. Gromov, A.V. Koshkin, T. Valova,
M.V. Alfimov, A.V. Feofanov, I.S. Alaverdian, V.A. Lokshin, A. Samat,
R. Guglielmetti, R.B. Girling, J.N. Morre and R.E. Hester, New J. Chem., 2002,
26, 1137.
753. A. Grofcsik, P. Baranyai, I. Bitter, A. Grun, E. Koszegi, M. Kubinyi, K. Pal and
T. Vidoczy, J. Mol. Struct., 2002, 614, 69.
754. O.A. Fedorova, Y.V. Federov, A.I. Vedernikov, O.V. Yescheulova, S.P. Gromov,
M.V. Alfimov, L.G. Kuz’mina, A.V. Churakov, J.A.K. Howard, S.Yu. Zaitsev,
T.I. Sergeeva and D. Moebius, New J. Chem., 2002, 26, 543.
755. O.A. Fedorova, S.P. Gromov and M.V. Alfimov, Russ. Chem. Bull., 2001, 50, 1970.
756. I. Baldea, I. Panea and A.C. Apetri, Studia Universitatis Babes-Bolyai, Chemia,
1999, 44, 117.
757. P.J.G. Coutinho, E.M.S. Castanheira, M.C. Rei and E.C.M. Oliveira, Ann. Rep.-Conf.
Insul. Dielectric Phenom., 1999, 2, 512.
758. Y. Su, X. Liao and S. Li, Huxaue Yanjiu Yu Yingyong, 2002, 14, 69.
759. N.M.F.S.A. Cerqueira, C.A.M.F. Oliveira, P.J. Coelho, L.H. Melo de Carvalho,
A. Samat and R. Guglielmetti, Helv. Chim. Acta, 2002, 85, 442.
760. V.K. Gupta and M.S. Kang, Polym. Prep. (Am. Chem. Soc., Div. Polym. Chem.),
2002, 43, 338.
761. C. Goretzki and H. Rititer, e-Polymers, 2002, Paper 19.
762. X. Liu, X. Wang and D. Liu, Gaofenzi Xuebao, 2001, 6, 773.
763. K. Hara, Setchaku, 2001, 45, 9.
764. Y. Taru, Shikizai Kyokaishi, 2000, 73, 607.
765. S.Sh. Rashidova, B.L. Oksenendler and N.N. Turaeva, Dokl. Akad. Nauk Resp.
Uzb., 2000, 3, 41.
766. N.D. Searle, Environ. Sci. Pollution Control Ser., 2000, 21, 605.
767. P. Hrdlovic, Polym. News, 2002, 27, 51.
768. P.P. Klemchuk, Environ. Sci. Control Ser., 2000, 21, 461.
769. A. Torikai, Environ. Sci. Control Ser., 2000, 21, 573.
770. O. Koyashiki and I. Toyama, Seibunkaisei Kemikarusu to Purasuchikku, 2000, 240,
108.
771. P. Dubois, Chim. Nouv., 2001, 19, 3297.
772. N.C. Billingham, Mater. Sci. Technol., 2000, 19, 469.
773. K. Anita, R.S. Roy and H.K. Jha, Acta Ciencia Indica, Phys., 2001, 27, 195.
Photochemistry, 36, 2007, 232–298 293

777. H. Kaczmarek, A. Kaminska, J. Kowalonek and A. Szalla, Mol. Cryst. Liq. Cryst.
Sci., Technol. Sect. A., 2000, 354, 421.
778. K. Scott and M. McGreer, Polyolefins 2001, Int. Conf. Polyolefins, Houston, Texas,
Feb 25th-28th, 2001, 471.
779. M.Ya. Mel’nikov, Chin. J. Polym. Sci., 2001, 19, 167.
780. J. Boxhammer, Macromol. Symp., 2002, 178, 11.
781. J.W. Summer and E.B. Rabinovich, Polym. Prep. (Am. Chem. Soc., Div. Polym.
Chem.), 2001, 42, 860.
782. D.C. Wright, Rapra Rev. Rep., 2001, 11, 1.
783. G.I. Stegman, A.G. Van-Gonzales, M. Canva, R. Twieg, A.C. Kowalczyk,
X.Q. Zhang, H.S. Lackritz, S. Marder, S. Thayumanavan, K.P. Chan, A.K.Y. Jen
and X. Wu, MCLC S&T, Sect. B: Nonlinear Opt., 2000, 25, 57.
784. S. Commereuc, L. Gonon, J.L. Gardette and V. Verney, Proc. Int. Congr. Rheol.,
13th., 2000, 1, 144.
785. I.I. Eyenga, W.W. Focke, L.C. Prinsloo and A.T. Tolmay, Macromol. Symp.,
2002, 178, 139.
786. J.W. Chin, J. Martin, E. Byrd, E. Embree and J.D. Tate, Polym. Prep. (Am. Chem.
787. T. Grossetete, L. Gonon and V. Verney, Polym. Degrad. Stabil., 2002, 78, 203.
788. F. Yu and S. Yao, Wuhan Huagong Xueyuan Xuebao, 2001, 23, 5.
789. Y.T. Yang and M.Y. Liao, Suliao Keji, 2002, 1, 7.
790. Q. Chen, Q. Qian and L. Xiao, Suliao, 2001, 30, 13.
791. F. Yu, Y. Liu and S. Yao, Polymer, 2002, 34, 302.
792. T.J. Turton and J.R. White, J. Mater. Sci., 2001, 36, 4617.
793. M.C. Pascu, M.M. Macoveanu, C. Vasile, A. Ioanid and R.C. Oghina, Cellulose
Chem. Technol., 2001, 34, 399.
794. P. Liu, W. Xu, P. Fan, S. Qian and L. Luo, Gaofenzi Cailiao Kexue Yu Gongcheng,
2002, 18, 63.
795. A.K. Bhowmick, J. Heslop and J.R. White, J. Appl. Polym. Sci., 2002, 86, 2393.
796. R. Wilken, A. Hollander and J. Behnisch, Plasmas Polym., 2002, 7, 19.
797. R. Wilken, A. Hollander and J. Behnisch, Plasmas Polym., 2002, 7, 185.
798. S. Wu and X. Xu, Yingyong Huaxue, 2001, 18, 758.
799. T.F. Abbasov and M.A. Salamanov, Plasticheskie Massy, 2002, 1, 23.
800. S.I. Kuzina and A.I. Mikhailov, Eur. Polym. J., 2001, 37, 2319.
801. K. Subramanian, Eur. Polym. J., 2002, 38, 1167.
802. S.D. Maksim’yuk, D.Y. Stavichna, J.R. White and O.V. Shiichuk, Ukr. Khim. Zh.,
2001, 67, 126.
803. H. Ma, S. Wang, B. Cui, W. Gao, W. Liu, S. Wang, H. ma, S. Ao, W. Deng and
J. Xu, Mater. Res. Soc., 2002, 700, 179.
804. E. Young, Ann. Techn. Conf., SPE., 60th, 2002, 2920.
805. F. Yao, Y. Bai and J. Meng, Gaofenzi Cailiao Kexue Yu Gongcheng, 2002, 18, 176.
806. W. Stevenson and J.R. White, J. Mater. Sci., 2002, 37, 1091.
807. Y. Xing and D. Wang, Cailiao Kexue Yu Gongyi, 1998, 62, 106.
808. R.P. Singh, A.V. Prasad and S.S. Solansky, J. Appl. Polym. Sci., 2002, 85, 1676.
809. J.T. Goldback, T.P. Russell and J. Penelle, Polym. Prep. (Am. Chem. Soc., Div.
Polym. Chem.), 2002, 43, 470.
810. M. Lazzari, M. Aglietto, V. Castelvetro and O. Chiantore, Polym. Degrad. Stabil.,
2003, 79, 345.
811. H. Kaczmarek, D. Drag, M. Swiatek and D. Oldak, Surf. Sci., 2002, 507, 877.
294 Photochemistry, 36, 2007, 232–298
812. Q. Chen, Q. Qian and L. Xiao, Jiegou Huaxue, 2001, 20, 508.
813. H. Kaczmarek, J. Kowalonek and D. Oldak, Polym. Degrad. Stabil., 2003, 79, 231.
814. M. Matsui, C.A. Schehr, J.J. Valentini and J.N. Weber, Polymer, 2002, 42, 5625.
815. I. Liakatas, M. Jager, C. Bosshard, P. Gunter and T. Kaino, MCLC S&T, Sect. B:
Nonlinear Opt., 2000, 25, 241.
816. K. Ha and J.L. West, J. Appl. Polym. Sci., 2002, 86, 3072.
818. H.Y. Low, Thin Solid Films, 2002, 413, 160.
819. S.K. Gupta, J.R. Sargeant and W.P. Weber, Polymer, 2001, 43, 29.
820. X.F. yang, D.E. Tallman, G.P. Bierwagen, S.G. Croll and S. Rohlik, Polym.
Degrad. Stabil., 2002, 77, 103.
821. S. Commereuc and V. Verney, Polym. Degrad. Stabil., 2002, 78, 561.
822. J.G. Bokria and S. Schlick, Polymer, 2002, 43, 3239.
823. P.M. Sathyanarayana, G. Shariff, M.C. Thimmegowda, M.B. Ashalatha,
R. Ramani and C. Ranganathaiah, Plast. Rubber Composites, 2002, 78, 449.
824. K.R. Millington and L.J. Kirschenbaum, Coloration Technol., 2002, 118, 6.
825. G.J.M. Fechine, R.M. Souto-Maior and M.S. Rabello, J. Mater. Sci., 2002, 37,
4979.
826. M. Wegelin, S. Canonica, A.C. Alder, D. Marazuela, M.J.F. Suter, T.D. Bucheli,
O.P. Haefliger, R. Zenobi, K.G. McGuigan, M.T. Kelly, P. Ibrahim and
M. Haefliger, J. Water Supply: Res. Technol., 2001, 50, 125.
827. S.I. Lee, S.H. Sur, K.M. Hong, Y.S. Shin, S.H. Jang, B.S. Kim and B.Y. Shin,
Kongop Hwahak, 2001, 12, 868.
828. S. Machida and K. Horie, Kobunshi Ronbunshu, 2002, 59, 725.
829. E. Andreou, A. Athanassiou, D. Fragouli, D. Anglos and S. Georgiou, Laser
Chem., 2002, 20, 1.
830. H. Niino, A. Miyabo, H. Yanase and A. Yabe, J. Photopolym. Sci. Technol., 2002,
15, 65.
831. M. Kunz and M. Bauer, Farbe Lacke, 2001, 107, 54.
832. T. Katoh, D. Yamaguchi, Y. Satoh, S. Ikeda, Y. Aoki, M. Washio and Y. Tabata,
Appl. Surf. Sci., 2002, 186, 24.
833. A. Quaranta, A. Vomiero, S. Carturan, G. maggioni and M.G. Della, Nucl. Instr.
Met. Phys. Res., Sect. B: Beam Interact. Mater. Atoms, 2002, 191, 680.
834. A. Laissar, V. Hizhnyakov, J. Kikas, A. Kuznetsov and A. Suisalu, Diff. Defect
Data – Solid State Data, Part A: Defect Diff. Forum, 2002, 208, 129.
835. Z. Geretovsky, B. Hopp, I. Beroti and I.W. Boyd, Appl. Surf. Sci., 2002, 186, 85.
836. T. Lippert, C. David, M. Hauer, T. Masubuchi, H. Masuhara, K. Nomura,
O.R.J. Nuyken, C. Phipps, J. Robert, T. Tada, K. Tomika and A. Wokaun, Appl.
Surf. Sci., 2002, 186, 14.
837. T. Lippert, J.T. Dickinson, M. Hauer, G. Kopitkovas, S.C. Langford, H. Ma-
suhara, O.R.J. Nuyken, H. Salmio, T. Tada, K. Tomita and A. Wokaun, Appl.
Surf. Sci., 2002, 197, 746.
838. A. Sionkowska, H. Kaczmarek, S. Vicini, E. Pedemonte and M. Wisniewski,
Polym. Degrad. Stabil., 2002, 78, 175.
839. L.M. Laurent and D.P. Kamdem, Polym. Eng. Sci., 2002, 42, 1657.
840. C. Bonini, M. D’Auria and R. Ferri, Photochem. Photobiol. Sci., 2002, 1, 570.
841. A. Wojciak, M. Sikorski, R. Gonzalez, J.L. Bourdelande and F. Wilkinson, Wool
Sci. Technol., 2002, 36, 187.
842. M. Paulsson, L.A. Lucia, A.J. Ragauskas and C. Li, J. Wood Chem. Technol.,
2001, 21, 343.
Photochemistry, 36, 2007, 232–298 295
843. M. Paulsson and R. Simonson, Chem. Mod Prep. Usage Lignin, ed.
T.Q. HuKluwer Academic Pub., N.Y., 2002, 221.
844. H.T. Chang and S.T. Chang, Polym. Prep. (Am. Chem. Soc., Div. Polym. Chem.),
2002, 43, 1303.
845. T.Q. Hu and B.R. James, Chem. Mod Prep. Usage Lignin, ed. T.Q. Hu, Kluwer
Academic Pub., N.Y., 2002, 247.
846. D.F. Guay, B.J.W. Cole, R.C. Fort, M.C. Hausman, J.M. Genco and T.J. Elder,
J. Pulp Paper Sci., 2002, 28, 217.
847. H.T. Chang, T.F. Yeh and S.T. Chang, Polym. Degrad. Stabil., 2002, 77, 129.
848. C.A. Lukey, D.J.T. Hill and P.J. Pomery, Polym. Degrad. Stabil., 2002, 78, 485.
849. T. Nguyen, J. Martin, E. Byrd and N. Embree, J. Coatings Technol., 2002, 74, 65.
850. T. Ishigaki, W. Sugano, M. Ike, H. Taniguchi, T. Goto and M. Fujita, Polym.
Degrad. Stabil., 2002, 78, 505.
851. G.F. Tjandraatmadja, l.S. Burn and M.C. Jollands, Polym. Degrad. Stabil., 2002,
78, 435.
852. A.W. Signor, M.R. VanLandingham and J.W. Chin, Polym. Degrad. Stabil., 2003,
79, 359.
853. J. Pospisil, S. Nespurek, H. Zweifel and J. Kuthan, Polym. Degrad. Stabil., 2002,
78, 251.
854. C. Decker, K. Zahouily and A. Valet, J. Coatings Technol., 2002, 74, 87.
855. M.E. Nichols and J.L. Tardiff, ACS Symp. Ser., 2002, 805, 373.
856. M.E. Nichols, C.M. Seubert and G.L. Gerlock, RadTech Rep., 2001, 15, 20.
857. L. Guillot, C. Dubois, L. Monney and J. Vebrel, Ann. Composites, 2001, 1, 101.
858. P. Delobelle, L. Guillot, C. Dubois and L. Monney, Polym. Degrad. Stabil., 2002,
77, 465.
860. K.K. Okudaira, H. Yamane, K. Ito, M. Imamura, S. Hasegawa and N. Ueno,
Surf. Rev. Lett., 2002, 9, 335.
861. I.I. Eyenga, w.W. Focke, L.C. Prinsloo and A.T. Tolmay, S. African J. Sci., 2001,
97, 359.
862. F. Lin, S.Z. Cheng and F.W. Harris, Polymer, 2002, 43, 3421.
863. Y. Yin, X. Zhou and F. Wen, Hubei Huagong, 2002, 19, 9.
864. T. Endo, Kemikaru Enjiniyaringu, 2001, 46, 516.
865. S.F. Dinetz, E.J. Bird and A.W. Fountain, J. Anal. Appl. Pyrolysis, 2002, 63, 241.
866. D.Y. Stavichna, O. Chiantore and A.V. Shiychuk, Kompozitsiini Polimeri Mate-
riali, 2000, 22, 118.
867. J.W. Martin, T. Nguyen, E. Byrd, B. Dickens and N. Embree, ACS Symp. Ser.,
2002, 805, 119.
868. L.I. Kolontain and L.B. Ignat’eva, Fibre Chem., 2001, 33, 29.
869. K. Kikkawa, Kotinguyo Tenkazai no Saishin Gijutsu, 2001, 127.
870. L. Davis, B. Sanders, J. Zenner and J. Stretanski, SPE Polyolefins 2002 Int. Conf.
Polyolefins, Houston, Texas, Feb. 24-27th, 2002, 195.
871. H. Ban, Z. Chao, L. Wang and L. Chen, Fushun Shiyou Xueyan Xuebao, 2002, 22,
19.
872. D. Leppard, P. Hayoz, T. Schafer, T. Vogel and F. Wendeborn, Chimia, 2002, 56,
216.
873. H. Yamazaki, Purasuchikkusu Eji, 2002, 48, 102.
874. H. Yamazaki, Porima Daijesuto, 2002, 54, 44.
875. L. Zhao, Zhongguo Suliao, 2001, 15, 74.
876. W. Lipinski and J. Ogonowski, Chemik, 2001, 54, 179.
296 Photochemistry, 36, 2007, 232–298
877. J. Yu, Gongcheng Sui Yingyong, 2001, 29, 30.

878. C. Krohnke and F. Werner, Rapra Rev. Rep., 2001, 11, 1.
879. F. Cangelosi, L. Davis and S.B. Samuels, J. Vinyl Additive Technol., 2001, 7, 123.
880. P. Solera and G. Capocci, SPE Polyolefins 2002 Int. Conf. Polyolefins, Houston,
Texas, Feb. 24-27th, 2002, 699.
881. B.M. Sanders, SPE Automotive TPO Global Conf., 2nd, MI, USA Oct 2-4th, 2000,
347.
882. K. Wang and X. Li, Zhongguo Suliao, 2001, 15, 1.
883. I.V. Germashev, V.E. Derbisher, M.N. Tsapleva and E.V. Derbisher, Russ. Polym.
News, 2001, 6, 53.
884. H. Yamanoi, Porima Daijesuto, 2002, 54, 35.
885. C. Decker and K. Zahouily, Radiat. Phys. Chem., 2002, 63, 3.
886. K. Yoshikawa, Setachaku no Gijitsu, 2001, 21, 41.
887. P. Arnaboldi, L. Davis, S.B. Samuels, J.M. Zenner and I. Vulvic, Polym. Polym.
Composites, 2002, 10, 93.
888. D. Ganz, Popular Plast. Packaging, 2002, 47, 70.
889. C. Decker, J. Vinyl Additive Technol., 2001, 7, 235.
890. S. Zeren, Macromol. Symp., 2002, 187, 343.
891. R.V. Todesco and N. Ergenc, Chimia, 2002, 56, 225.
892. Q. Wang, B. Qu and Q. Wu, Gaoedeng Xuexiao Huaxue Xuebao, 2001, 22, 1610.
893. M. Danko, S. Chmela and P. Hrdlovic, Polym. Degrad. Stabil., 2003, 79, 333.
894. M. Lucarini, G.F. Pedulli, D. Lazzari, M. Vitali and S.M. Andrews, Macromol.
Chem., 2002, 203, 2239.
895. H. Nakatani, N. Kaihatsu, B. Liu, M. Terano and E. Tobita, Materiaru Raifu
Gakkaishi, 2001, 13, 185.
896. X. Liu, J. Yang and Y. Chen, Polym. Adv. Mater., 2002, 13, 247.
897. G.J. Sun, H.J. Jang, S. Kaang and K.H. Chae, Polymer, 2002, 43, 5855.
898. H.S. Kim and K.H. Chae, Polymer (Korea), 2001, 25, 625.
899. P. Gijsman, Polymer, 2002, 43, 1573.
900. D. Muller, Res. Discl., 2001, 451, P1821.
901. M. Stein, J. Keck, F. Waiblinger, A.P. Fluegge, H.E.A. Kramer, A. Hartschuh,
H. Port, D. Leppard and G. Rytz, J. Phys. Chem., 2002, 106, 2055.
902. V. Bojinov and I. Grabchev, J. Photochem. Photobiol., Part A, 2002, 150, 223.
903. J.E. Pickett, ACS Symp. Ser., 2002, 805, 250.
904. A.D. DeBellis, R. Iyengar, N.A. KAprinidis, R.K. Rodebaugh and J. Suhadolink,
ACS Symp. Ser., 2002, 805, 453.
905. V.N. Serova, O.A. Cherasova, E.N. Chezova, N.A. Mukmeneva and V.P. Ark-
hireev, Russ. Polym. News, 2001, 6, 1.
906. S. Knaus, A. Nennadal and B. Froschauer, Macromol. Symp., 2001, 176, 223.
907. S.G. Guseva, O.B. Ushakova, V.D. strygin and E.E. Potapov, Kauchuk i Rezina,
2001, 6, 13.
908. L. Zheng, W. Shu, X. Shen and Z. Zhou, Xiandai Suliao Jiagong Yingyong, 2001,
13, 38.
909. S.A. Siling, A.L. Margolin, I.Y. Kalontarov, S.V. Vinogradova, F.F. Niyazi,
Y.V. Chaiko and S.S. Dzhumaev, Synth. Prop. Heterocycl. Cmpnd., ed. S.A. Siling
and G.E. Zaikov, Nova Science Pub., N.Y., 2001, 1.
910. J.L. Thomas, Dyes Pigments, 2002, 53, 195.
911. W.N. Sisk, N. Ono, T. Yano and W. Wada, Dyes Pigments, 2002, 55, 143.
912. T. Hihara, Y. Okada and Z. Morita, Dyes Pigments, 2002, 53, 153.
913. H. Tian and S. Yang, J. Photochem. Photobiol., Part C, 2002, 3, 67.
Photochemistry, 36, 2007, 232–298 297
914. H. Oda, Nippon Kasei Gakkaishi, 2002, 53, 271.

915. H. Oda, Text. Res. J., 2001, 71, 1057.
916. N. Sekar, Colourage, 2001, 48, 56.
917. S. Yang, F. Meng, H. Tian and K. Chen, Eur. Polym. J., 2002, 38, 911.
918. F. Chen, J. He, J. Zhao and J.C. Yu, New J. Chem., 2002, 26, 336.
919. X. Shang, X. Gong, H. Xiao and H. Te, Fenzi Kexue Xuebao, 2001, 17, 193.
920. P.N. Thanki and R.P. Singh, Macromol. Mater. Eng., 2001, 286, 756.
921. A. Planner, T. Runka, A. Skrzypczak, M. Hara and J. Miyake, Proc. SPIE-Int.
Soc. Opt. Eng., 2001, 4238, 250.
922. J. Oakes, Rev. Prog. Col. Rel. Top., 2001, 31, 21.
923. H. Oda, Col. Technol., 2001, 11, 257.
924. M.M. Kamel, M. Mo and M.A. El-Apasery, J. Text. Assoc., 2001, 62, 29.
925. A.A. Krasnovsky, M.E. Bashtanov, N.N. Drozdova, O.A. Yuzhakova and E.A.
Luk’yanets, Quantum Electronics, 2002, 32, 83.
926. N.B. Sokolova, L.P. Kovzhina, N.M. Dmitrieva and N.V. Blinova, Russ. J. Appl.
Chem., 2002, 75, 254.
927. S.N. Amujigu, J. Chem. Soc. Nigeria, 2001, 26, 102.
928. T. Rijavec, S.M. Kveder and E. Vujasinovic, Tekstil, 2001, 50, 277.
929. R.P. Ponomareva, O.P. Studzinskii and L.M. Borisova, Russ. J. Gen. Chem., 2002,
72, 1104.
930. M. Shimodori, K. Kohmoto and M. Saito, Sen’I Gakkaishi, 2002, 58, 1.
931. T. Masui, G. Adachi, M. Tanaka, M. Oda, T. Doi, T. Kawamata and
A. Fujishima, Nanomateriaru no Saishin Gijutsu, 2001, 35, 601.
932. N. Sendoda, Kogyo Zairyo, 2001, 49, 45.
933. C. Konno and K. Kosaka, Kogyo Toso, 2001, 171, 25.
934. C. Xu, Guangdong Huagong, 2001, 28, 19.
935. Y. Ohko and A. Fujishima, Kemikaru Enjiniyaringu, 2002, 47, 275.
936. P. Boudry, Caoutchoucs Plastiques, 2001, 797, 65.
937. N.D. Konovalova and V.N. Mistchenko, Kataliz I Neftekhimiya, 2001, 9, 84.
938. S. Sawano, Bosei Kanri, 2001, 45, 224.
939. L. Davis, B. Sanders and J. Stretanski, Your Ticket to Outstanding Color and
Additives, Conf. Arlington, VA, USA., Sept. 17-19th, SPE., 2000, 9, 173.
940. M. Saquib and M. Muneer, Col. Technol., 2002, 118, 307.
941. M. Chen, N. Ao, Y. Chen, J. Qu, C. Wang, H. Zhou and H. Qian, Dianzai Xianwei
Xuebao, 2001, 20, 385.
942. S.l. Pugh and J.T. Guthrie, Dyes Pigments, 2002, 55, 109.
943. S.V. Manorama, K. Reddy, C.V.G. Reddy, S. Narayanan, P.R. Raja and P.R.
Chatterji, J. Phys. Chem. Solids, 2001, 63, 135.
944. T.J. Kemp and R.A. McIntyre, Prog. React. Kinet. Mech., 2001, 26, 337.
945. Y. Iguchi, H. Ichiura, T. Kitaoka and H. Tanaka, Quantum Electron., 2002, 32,
162.
946. J. Searle and D. Worsley, Plast. Rubber Composites, 2002, 31, 329.
947. P.A. Christensen, A. Dilks, T.A. Edgerton, E. J. Lawson and J. Temperley,
J. Mater. Sci., 2002, 37, 4879.
948. N.S. Allen, M. Edge, G. Sandoval, A. Ortega, C.M. Liauw, J. Stratton and R.B.
McIntyre, Polym. Degrad. Stabil., 2002, 76, 305.
949. N.S. Allen, M. Edge, A. Ortega, C.M. Liauw, J. Stratton and R.B. McIntyre,
Polym. Degrad. Stabil., 2002, 78, 467.

W Ts 8 U1 P2

Caricato da

Informazioni sul documento

Descrizione originale:

Titolo originale

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

W Ts 8 U1 P2

Caricato da

Copyright:

Formati disponibili

Photochemistry

A Review of the Literature Published between

r The Royal Society of Chemistry 2007

All rights reserved

Published by The Royal Society of Chemistry,

Registered Charity Number 207890

For further information see our web site at www.rsc.org

Typeset by Macmillan India Ltd, Bangalore, India

Introduction and Review of the Year 1

Photolysis of Carbonyl Compounds 9

1 Norrish Type I Reactions 10

Enone Cycloadditions and Rearrangements:

Photochemistry of Alkenes, Alkynes and Related Compounds 55

Photochemistry of Aromatic Compounds 91

Photooxidation and Photoreduction 133

3 Elimination of Nitrogen from Diazo

Polymer Photochemistry 232

4.11 Natural Polymers 265

This is a very special volume of Photochemistry, because it is to be the last in

Deserving special recognition for his contribution is Andrew Gilbert,

(3) X = CO2Et, COMe, CN (4)

(5) R = CO2 H3NR* (6)

The photocycloaddition of aldehydes to the 5-methoxyxoxazole (7) has been

The irradiation of CBr4 in MeOH has been reported as an efﬁcient photo-

(13) a: R-R = CMe2 (14) a: R = Tf

Photocyclizations of mono- and distyryl substituted polynuclear arenes in

The triﬂuoromethyl group has long been considered as having a low

(28) (29) (30)

A very good example of the enormous beneﬁts that DFT computations of

Wavelength dependent differential release of compounds from a solid-phase

There is little doubt that photochemically induced single electron-transfer

1 Norrish Type I Reactions

a-Fission processes are commonly brought about by the irradiation of alde-

As mentioned earlier in this chapter, irradiations within zeolites continue to

Irradiation of the ketone (6) in argon-degassed cyclohexane brings about

2 Norrish Type II Reactions

The benzaldehyde derivative (14) undergoes Norrish Type II hydrogen

Norrish Type II hydrogen abstraction is the predominant reaction on irradia-

2.2 Other Hydrogen Transfers. – A full account of the photochemical reaction

Griesbeck41 has published an account of how stereoselectivity in single and

The sensitizer dependency for the cycloreversion of trans,trans-2,3-diphenyl-

A mixture of carbohydrates is formed on irradiation of formaldehyde at 77 K.

4.1 Decarboxylation and Decarbonylation. – The potential energy surfaces for

The photoreactivity of indoprofen is centred on the propionic acid moiety

Pyruvic acid undergoes elimination of an OH radical on irradiation at 193

4.2 Reactions of Miscellaneous Haloketones and Acid Chlorides. – UV irradia-

a-Iodoketones (45) undergo facile conversion to the corresponding a-

The SET-induced ring opening of the cyclopropyl moiety in (49) results in

Kakiuchi1 has reviewed some recent advances in enantioselective (2 þ 2)- and (2

1.1 Intermolecular Cycloadditions

The photochemical (2 þ 2)-dimerization between trans-cinnamates contained

The photochemical addition of methyl 2,3-dioxopentanoate to terpinolene

Photocycloaddition of dimethyl cyclobut-1-ene dicarboxylate to cyclohexene

1.1.2 Intermolecular Additions to Cyclopentenones and Related Systems.

structures obtained are claimed to be in good agreement with the diastereo-

1.1.3 Intermolecular Additions to Cyclohexenones and Related Systems. Cal-

Margaretha and co-workers20 have described the cycloaddition of some

1.2 Intramolecular Cycloadditions. – (2 þ 2)-Photocycloaddition within the

1.2.1 Intramolecular Additions to Cyclopentenones and Related Systems. The

1.2.2 Intramolecular Additions to Cyclohexenones and Related Systems. 3–

2.1 a,b-Unsaturated Systems

The photoisomerization of retinal has been studied using super-short light