Introduction

Introduction to Photochemical
Reactions and Processes
Faculty Chemistry
Authors
Fabian Guba
Pascal Hermann
Maximilian Sender
Ümit Tastan
Benjamin Wriedt
Dirk Ziegenbalg
Stuttgart, May 19, 2017

Contents
1 Foreword 1
2 Theoretical Part 3
2.1 Photochemical Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.1 Electromagnetic Radiation . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.2 Wave–Particle Duality . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.3 B EER -L AMBERT-Law . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.1.4 Models of Chemical Bonds . . . . . . . . . . . . . . . . . . . . . . . . 7
2.1.4.1 Molecular Orbital Theory . . . . . . . . . . . . . . . . . . . 7
2.1.4.2 Ligand Field Theory . . . . . . . . . . . . . . . . . . . . . . 9
2.1.5 Interaction of Light with Chemical Bonds . . . . . . . . . . . . . . . . 14
2.1.5.1 General Considerations . . . . . . . . . . . . . . . . . . . . 14
2.1.5.2 Energy of Photons . . . . . . . . . . . . . . . . . . . . . . . 14
2.1.5.3 F RANCK -C ONDON Principle . . . . . . . . . . . . . . . . . 14
2.1.5.4 JABLONSKI Diagram . . . . . . . . . . . . . . . . . . . . . 16
2.1.5.5 Charge-Transfer . . . . . . . . . . . . . . . . . . . . . . . . 16
2.1.6 Relations Between Chemical Structure and Electron Spectra . . . . . . 17
2.1.7 W OODWARD -H OFFMANN Rules . . . . . . . . . . . . . . . . . . . . 19
2.2 Reaction Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.2.1 Cycloadditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.2.1.1 General Concept . . . . . . . . . . . . . . . . . . . . . . . . 23
2.2.1.2 [4+2]-Cycloadditions (D IELS -A LDER-Reactions) . . . . . . 23
2.2.1.3 [2+2]-Cycloadditions . . . . . . . . . . . . . . . . . . . . . 24
2.2.2 Photooxygenations and S CHENCK-En-Reactions . . . . . . . . . . . . 25
2.2.3 N ORRISH Type I and Type II Reactions . . . . . . . . . . . . . . . . . 28
2.2.3.1 Norrish Type I Reactions . . . . . . . . . . . . . . . . . . . 28
2.2.3.2 Norrish Type II Reactions . . . . . . . . . . . . . . . . . . . 30
2.2.3.3 Norrish Type I Reactions vs. Norrish Type II Reactions . . . 31
Contents
2.2.4 BARTON Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

2.2.5 Photolysis of Azido Compounds . . . . . . . . . . . . . . . . . . . . . 32
2.2.6 Photonitrosylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.2.7 Photohalogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.2.7.1 General Aspects . . . . . . . . . . . . . . . . . . . . . . . . 36
2.2.7.2 Photochlorination . . . . . . . . . . . . . . . . . . . . . . . 37
2.2.7.3 Photobromination . . . . . . . . . . . . . . . . . . . . . . . 38
2.2.8 Photosulfochlorination and Photosulfoxidation . . . . . . . . . . . . . 39
2.2.9 Photodesulfonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2.2.9.1 General Aspects . . . . . . . . . . . . . . . . . . . . . . . . 41
2.2.9.2 Desulfonation or Substitution of a Sulfonyloxy Group by a
Hydrogen Atom . . . . . . . . . . . . . . . . . . . . . . . . 42
2.2.9.3 Substitution of a Sulfonyloxy Group by Another Functional
Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
2.2.9.4 Dimerization Under Desulfonation . . . . . . . . . . . . . . 43
2.2.10 Photodecarbonylation . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2.2.11 Photochemical Reactions of Metal Complexes . . . . . . . . . . . . . 45
2.2.11.1 General Aspects . . . . . . . . . . . . . . . . . . . . . . . . 45
2.2.11.2 Photosubsitution Reactions . . . . . . . . . . . . . . . . . . 46
2.2.11.3 Photooxidation-Reduction Reactions . . . . . . . . . . . . . 47
2.2.12 Photoinduced Radical Polymerization . . . . . . . . . . . . . . . . . . 48
2.2.13 Cationic Photopolymerization . . . . . . . . . . . . . . . . . . . . . . 48
2.2.14 Photoinduced Polyaddition for the Synthesis of PUR . . . . . . . . . . 50
2.2.15 Photoinduced Ring Opening Metathesis of Cyclic Olefines . . . . . . . 52
2.2.16 Photohydrodimerization . . . . . . . . . . . . . . . . . . . . . . . . . 54
2.2.17 Photocatalytic Water Splitting . . . . . . . . . . . . . . . . . . . . . . 56
2.2.18 Phototransduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
2.2.19 Photosynthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
2.3 Technical Aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
2.3.1 Light Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
2.3.1.1 General Aspects . . . . . . . . . . . . . . . . . . . . . . . . 65
2.3.1.2 Thermal Light Sources . . . . . . . . . . . . . . . . . . . . 67
2.3.1.3 Non-Thermal Light Sources . . . . . . . . . . . . . . . . . . 67
2.3.2 Optical Materials and Filter . . . . . . . . . . . . . . . . . . . . . . . 72
2.3.3 Reactor Types and Concepts . . . . . . . . . . . . . . . . . . . . . . . 73
2.3.3.1 Conventional Reactor Types . . . . . . . . . . . . . . . . . . 73
2.3.3.2 Microstructured Photoreactor . . . . . . . . . . . . . . . . . 75
2.3.4 Actinometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
2.3.4.1 General Information . . . . . . . . . . . . . . . . . . . . . . 77
2.3.4.2 The H ATCHARD-PARKER/Ferrioxalate Actinometer . . . . . 78
2.3.4.3 Other Chemical Actinometers . . . . . . . . . . . . . . . . . 79
2.3.5 Radiometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
2.3.6 Reaction Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
IV
Contents
2.3.7 Scale-Up Aspects of Photoreactors . . . . . . . . . . . . . . . . . . . . 84

2.3.8 Industrial Preparative Photochemical Processes . . . . . . . . . . . . . 85
2.3.9 Waste Water Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . 87
2.3.9.1 General Aspects . . . . . . . . . . . . . . . . . . . . . . . . 87
2.3.9.2 Contamination of Waste Water with Pharmaceuticals . . . . . 89
2.3.9.3 Advanced Oxidation Processes . . . . . . . . . . . . . . . . 90
2.3.9.4 Fenton Reaction and Photo-Fenton-Process . . . . . . . . . . 90
2.3.9.5 Photocatalytic Processes . . . . . . . . . . . . . . . . . . . . 91
3 Practical Part 93
3.1 Photoreactions in the Laboratory Course of Technical Chemistry . . . . . . . . 93
3.1.1 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
3.1.2 Experimental Procedure . . . . . . . . . . . . . . . . . . . . . . . . . 95
3.1.2.1 Preparation of the Spectrometer . . . . . . . . . . . . . . . . 96
3.1.2.2 UV/VIS Measurements . . . . . . . . . . . . . . . . . . . . 97
3.1.2.3 Reactor Startup . . . . . . . . . . . . . . . . . . . . . . . . 97
3.1.3 Evaluation of Experimental Data . . . . . . . . . . . . . . . . . . . . . 97
3.1.3.1 List of Equipment . . . . . . . . . . . . . . . . . . . . . . . 98
Bibliography 99
V
Foreword
1
Sunlight is the main energy source for green plants. The energy is stored as carbohydrates and
later on used for growing. The about 100 · 109 t of dry biomass that are produced every year by
photosynthesis illustrate the huge impact of photochemical processes in nature. Besides convert-
ing energy, photochemical reaction can also yield “value-added” chemicals. The biosynthesis of
vitamin D3 in the human skin is a prominent example.
While photochemical reactions are the foundation of life on earth, the application of photo-
chemical syntheses in chemical industries is seldom. This might be attributed to the interaction
of light with matter, that has to be considered in addition to the parameters that influence ther-
mally initiated reactions. As a consequence, designing photochemical processes on a technical
scale is more challenging than the development of conventional chemical processes. Further-
more, the availability of light sources, the scope of synthesis routes or the extent of education
with respect to photochemical processes might be reasoned.
In general, the significance of a certain research field in education goes along with either its
industrial relevance or its importance for fundamental research. Obviously, these two directions
of research are coupled to some degree. Tendentially, a chemical process of industrial impor-
tance will attract researcher’s attention more easily, even in the field of fundamental research
and renders a research topic attractive for funding. In contrast, the inverse coherence is much
harder to realize. Consequently, the small number of applications of photochemical processes in
industry raises hurdles for an intensification of research as well as education on photochemical
processes.
The limited access to free information on photochemical processes is another obstacle for in-
creasing the interest of young researchers in photochemical technology. While the open-access-
idea for scientific publications gains more and more supporters, basic information on the entire
field of photochemical processes are not available freely in a comprehensive and validated for-
mat. A well accepted example of such a comprehensive and validated format for general chem-
istry is the ChemgaPedia-platform, providing comprehensive knowledge and lectures on a broad
field of chemical topics.[1]
To negotiate the hurdles discussed above, this document aims on contributing a freely acces-
sible source of information on photochemical processes. The information are available online as
a Wikipedia/ChemgaPedia-type online service.[2] The different articles were also compiled as a
single document, which is available as a PDF.
At the time of first publication in spring 2017, the published articles cover a broad range of
topics, starting from photochemical principles through reaction types to technical aspects. The
scope of the single articles was chosen to give the reader a starting point for further investigations
in the scientific literature. Hence, the articles provide an overview of the single topics rather
than a discussion of all details. For delving into single topics, the reader is referenced to the
large number of excellent text books which are available. In addition to the theoretical chapter,
a chapter devoted to practical courses was added. The intention of this chapter is to provide
course manuals for experiments with photochemical background, allowing universities an easy
implementation of experiments in the curriculum.
It is self-evident, that the format of a Wikipedia was chosen to encourage the interested audi-
ence to provide further articles to this service as well as corrections or supplements of the already
published articles. Contributions can be send to photo-wiki@itc.uni-stuttgart.de.
New articles as well as corrections will be integrated into the online service and into the PDF
version.
The preparation of this document was made possible through financial support of the Fonds
der Chemischen Industrie im Verband der Chemischen Industrie e.V. (FCI)[3] and the Faculty of
Chemistry of the University of Stuttgart. I gratefully acknowledge this support, which allowed
to lay the foundation for a freely accessible compendium on photochemical processes.
Dirk Ziegenbalg
Stuttgart, 19.05.2017
2
Theoretical Part
2
2.1 Photochemical Principles
2.1.1 Electromagnetic Radiation
Electromagnetic radiation consists of two components: the electric and the magnetic field. It
can be described as electromagnetic waves, which are synchronized oscillations of magnetic
and electric fields and propagate with the speed of light through vacuum.
Electromagnetic radiation can be classified into classes comprising different types of inter-
action with matter. Distinction between the different classes can be made by the frequency f ,
wavelength λ or energy E of the radiation according to the P LANCK -E INSTEIN correlation:
h·c
Eλ = h · ν = , (2.1)
λ
with h being P LANCK’s constant (h = 6.626 · 1034 J s) and c being the speed of light (c = 299 792 458
m s−1 ). In general the following main classes of radiation are distinguished:
• γ (gamma) radiation (γ-ray),
• X-radiation (X-ray) ,
• ultraviolet radiation (UV),
• visible radiation/light (VIS),
• infrared radiation (IR) and
• radio waves.
A more detailed breakdown of the respective ranges can be found in Table 2.1 and Figure 2.1.
Table 2.1: Classes of electromagnetic radiation and the caused interaction.

name wavelength / m frequency / s−1 interaction
γ-ray < 10−11 > 1019 nuclear excitation
X-ray 10−11 – 10−9 1019 – 3 · 1017 excitation of core electrons
UV 10−9 – 4 · 10−7 3 · 1017 – 7.5 · 1014 excitation of valence electrons
VIS 4 · 10−7 – 7 · 10−7 7.5 · 1014 – 4.3 · 1014 excitation of valence electrons
IR 7 · 10−7 – 10−3 4.3 · 1014 – 1011 molecular vibrations
microwaves 10−3 – 10−1 1011 – 3 · 108 molecular rotations
radio waves > 10−1 < 3 · 108 molecular rotations
→ frequency ν / Hz
24 22 20 18 16 14 12 10 8
10 10 10 10 10 10 10 10 10 106 104 102 100
UKW MW LW
γ -ray X- UV IR microwave KW
ray radiowaves
10-16 10-14 10-12 10-10 10-8 10-6 10-4 10-2 100 102 104 106 108
wave length λ / m
UV VIS
200 300 400 500 600 700

wavelength λ / nm
Figure 2.1: The electromagnetic spectrum. The magnification illustrates the wavelength range
relevant for photochemical reaction. Based on.[4]
The way matter interacts with electromagnetic radiation depends on the wavelength of the
radiation. The essential requirement for an interaction is that the energy of the radiation is equal
to the difference of certain energy levels of the molecule. These can be either electronic or vi-
brational energy levels. The interacting molecule is excited to a higher energy level. Especially
electronic excitations are of interest for photochemical conversions. A change of the electronic
level corresponds to a change of the occupation of the molecular orbitals by valence electrons.
This results in a change of the chemical nature and reactivity. This can be utilized beneficially
to enter reaction pathways not accessible through thermal initiation, namely heating of the reac-
tants.
4
Figure 2.2: The double-slit experiment of Thomas YOUNG, with a being the light source, b and
c are slits in a screen and d is a screen on which an interference pattern can be
observed.[6]
2.1.2 Wave–Particle Duality
Wave Character: The experiments of Thomas YOUNG with a double slit in the beginning of
the 19th century finally lead to the acceptance of the wave character of light.[5] As shown in
Figure 2.2, this experiment resulted in an interference pattern on the screen with positive and
negative interference.
Particle Character: The theory on the particle character of light was already published in
the 17th and 18th century but was neglected after acceptance of the wave character of light
in the 19th century. But some effects could not be explained by considering light as a wave.
The particle character of light was brought into scientific discussion again by Einstein with his
explanation of the photoelectric effect.[7]
When metal plates are irradiated with light, it is possible to remove electrons from these
plates. In 1905 Einstein found, that this effect is not coupled to the intensity of the light but the
wavelength and thus the energy. His explanation of this observation by using Planck’s relation
(Equation 2.1) finally lead to the acceptance of the particle character of light.
Dualism: Electromagnetic radiation thus possess properties of both, a particle and a wave. It
is common to associate light with the properties of a wave, e.g. with scattering and diffraction.
Despite this, light also shows properties of a particle, e.g. a momentum by which Crookes
radiometer, also known as “solar mill”, can be driven. The correlation between wavelength λ
and momentum p can be described mathematically with the de-Broglie-correlation:[8]
h
λ= . (2.2)
p
5
For photochemistry, considering light as photons is in line with the amount based description
of chemical processes. Conversion of energy based quantities, often used to describe light, is
possible with equation Equation 2.1.
2.1.3 B EER -L AMBERT-Law
If a medium is irradiated three major processes may occur: i) absorption, ii) reflection and
iii) scattering. Absorption is the transfer of energy from an electromagnetic field to a material or
a molecular entity. Reflection describes the change of direction of the electromagnetic radiation
caused by a changing refractive index at an interface between two different media. Scattering
also causes a change of the direction of the radiation but is caused by localized non-uniformities
in a medium (e.g. an atom, particle, drop, etc.). The transmittance T , which is the fraction of
radiation received/detected after a particular medium, can be expressed as:
Pλ
T (l) = = f (λ , l) + ρ(λ , l) + σ (λ , l), (2.3)
Pλ0
with f (λ , l) being the absorption factor, which is the fraction of radiation absorbed by the sys-
tem, ρ(λ , l) being the reflectance, which is the fraction of radiation reflected by the system, and
σ (λ , l) being the fraction of light scattered by the system. All these terms of the sum depend on
the wavelength and the length/thickness of the irradiated system.
Irradiating a homogeneous medium perpendicular to the surface normal of the medium or
vessel (e.g. a cuvette or reactor) leads to the situation, that the terms describing reflection and
scattering do not contribute to the transmittance. Hence, the fraction of radiation passing through
the medium just depends on the absorption. The absorption process can be described by the
B EER -L AMBERT law: !
Pλ0
A(λ ) = lg = ε(λ )cl. (2.4)
Pλ
The absorbance A(λ ), being the logarithmic fraction of the incident Pλ0 to the transmitted spectral
radiant power Pλ , is equal to the product of the molar (decadic) absorption coefficient ε(λ ),
the concentration of the absorbing species c and the optical path length l. A commonly used
unit of ε(λ ) is dm mol−3 cm−1 (M−1 cm−1 ). This correlation holds true for diluted solutions,
where interactions between the absorbing species are negligible. This is typically the case if the
concentration is kept below approximately c = 0.01 M.
6
2.1.4 Models of Chemical Bonds
2.1.4.1 Molecular Orbital Theory
A fundamental knowledge of the electronic states in molecules or complexes is the foundation

of a thorough understanding of photochemical processes that these substances can undergo. The
molecular orbital theory provides such an understanding.
The molecular orbital theory assumes, that bonds between atoms are a linear combination of
the individual atom orbitals, forming the molecular orbitals. The electrons in a molecule are lo-
calized in these molecular orbitals. The theoretical foundation of this concept is the Schrödinger
equation.
The first assumption is, that core electrons of an atom or better the electrons in the inner shells
do not interact with the electrons of other atoms. These electrons are the so called non binding
electrons. Responsible for the interaction with other atoms are only the valence electrons, or
more precisely, the electrons in the outermost electronic shell of the atom. The Schrödinger
equation describes the electrons as a wave. Waves can interfere in two way with each other.
Firstly, constructive interference, that reduces the energy level of an orbital and secondly de-
structive interference, that increases the energy of an orbital. The electrons in the low energy
orbitals are called bonding electrons, the electrons in the high energy orbitals are called anti-
bonding electrons. An easy to imagine picture of the difference between a bonding and an
anti-bonding orbital is, that the electron density distribution is concentrated between the atom
cores for bonding orbitals. Despite this, the electron density of anti-bonding orbitals is not be-
tween the two nuclei. A non-bonding molecular orbital (NBMO) neither increases nor decreases
the bond order between the involved atoms (see Equation 2.5). Non-bonding orbitals are often
referred to by the letter n. The energy level of a non-bonding orbital is typically in between
the lower energy of a bonding orbital and the higher energy of a corresponding anti-bonding
orbital.[8]
The nature of the bond depends on the 3 dimensional probability density of the orbitals. It
is possible to distinguish between σ -orbitals, π-orbitals and δ -orbitals. σ -orbitals are orbitals
where the linear combination of the atomic orbitals (LCAO) lead to a cylindrical geometry. The
electron density is highest directly on the axis between the nuclei. This can be found for bonds
consisting of two s-orbitals or one s-orbital and one py -orbital (see Figure 2.3). π-orbitals are
orbitals where the two atom orbitals are orientated parallel and where two lobes of the atom
orbitals overlap. The p-orbital stands perpendicular to the σ -orbital. This can be the case for
two py or two pz orbitals (see Figure 2.3). δ -orbitals only occur by parallel orientation of two
d-orbitals, where all four lobes of the orbital overlap (e.g. two dxy -orbitals).[8] Examples of all
bonding-types are shown in figure 2.4.
7
s px py pz dxy dxz dyz dx2 −y2 dz2
Figure 2.3: Different atomic orbitals.
(a) (b) (c)
Figure 2.4: Electron density distributions of different bonding molecular orbitals: (a) σ -
orbital,[9] (b) π-orbital[10] and (c) δ -orbital.[11]
6σ ∗
6σ ∗
5π ∗
5π ∗
2p 2p 2p
px py pz px py pz px py pz
4π
2p
px py pz
Energy
Energy
4σ
3σ 3π
2σ ∗
2σ ∗
2s 2s 2s
2s
1σ
1σ
O O2 O C CN – N
(a) (b)
Figure 2.5: MO schemes of (a) O2 and (b) CN – molecule.[8]
8
Based on the G ROTRIAN-diagram, that shows the energetic level of the separate atomic or-
bitals, it is possible to create a MO-scheme with the newly created orbitals by the LCAO. The
MO-scheme of O2 and CN – are shown in Figure 2.5 as examples. The anti-bonding MOs are
illustrated with a ∗ , thus σ and π are the bonding orbitals, σ ∗ and π ∗ the anti-bonding orbitals.
It is possible to calculate a bond order b with the following equation:
1
b = (n − n∗ ), (2.5)
2
with n being the bonding electrons and n∗ the anti-bonding electrons. As obvious in the MO-
scheme, a higher b means a more stable molecule due to the lower energy level.
The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecule orbital
(LUMO) are of special interests. For the example of CN – , the HOMO is the 4σ -orbital and
the LUMO is the 5π ∗ -orbital as shown in the MO scheme in figure 2.5 (b). HOMO-LUMO
transitions are typical in photochemistry.
For more detailed information on the molecular orbital theory, the reader should refer to text-
books of general chemistry.
2.1.4.2 Ligand Field Theory
The ligand field theory (LFT) describes the interaction of the ligand’s electron pairs with the
d-orbitals of the central transition metal. A bunch of physical and chemical properties like
magnetic behavior, absorption spectra and preferred occurrence of oxidation numbers and coor-
dinations can be explained by this theory.[12]
A transition metal (ion) possesses five d-orbitals. The five d-orbitals are the dz2 , dx2 −y2 , dxy ,
dxz , dyz orbitals. Bringing a metal atom or ion into a (hypothetically) spherically symmetrical lig-
and field causes an elevation of the energy of the d-orbitals. Because interactions are identically
in all spatial directions, all d-orbitals have the same energy and the orbitals are still degenerated.
Real interactions between ligands and central metal atoms do not show a spherically sym-
metrical ligand field. Consequently, the energetic levels of the orbitals differ depending on the
geometrical position of the ligands as well as the properties of both, the ligand and the central
atom. In the following paragraphs, the characteristics of octahedral and tetrahedral complexes
will be discussed as examples. For information on other geometrical coordinations the reader
should refer to textbooks of inorganic chemistry.[12,13]
Octahedral Complexes In an octahedral complex, the transition metal ion in the center is
coordinated by 6 ligands, one ligand on each position of the axes of coordinates. As shown
in Figure 2.6, the interaction of the d-orbitals with the ligand orbitals differs depending on the
9
dxy dxz dyz
z z z
y y y
x x x
dx2 −y2 dz2
z z
= ligand
y y
x x
Figure 2.6: Octahedral coordination of d-orbitals.
orbital under consideration. Interaction of the orbitals dxy , dxz , dyz , that are lying between the
axes of coordinates, is less pronounced as for the orbitals dz2 and dx2 −y2 , that are lying on the
axes. This results in a separation of the d-orbitals in two groups with different energy levels as
shown in Figure 2.7. The dxy , dxz , dyz orbitals, referred to as t2g for symmetry reasons, have a
lower energy level as the dz2 and dx2 −y2 orbitals, referred to as eg states.
The energy difference between the t2g and the eg state equals ∆O = 10 Dq. Because the sum of
the orbital energies has to be equal to the energy of the spherically symmetrical ligand field, the
energy of the of the t2g orbitals is decreased by 2/5∆O and the energy of the eg is increased by
3/5∆O . This leads to a stabilization of the t2g orbitals and to a destabilization of the eg orbitals.
In total, the barycenter of the orbital energies is equal to the energy for a spherically symmetrical
ligand field. The overall energy increase of the d-orbitals in an octahedral complex compared
to the free ion depends on the ligands and metal ions and is around 20 eV to 40 eV, ∆O is in the
range of 1 eV to 4 eV.[12]
Tetrahedaral Complexes For complexes showing a tetrahedral coordination the situation is

different to that of an octahedral coordinated one. Interaction between the orbitals lying between
10
eg
6 Dq.
degenerate d-orbitals
∆O
4 Dq.
Energy
t2g
d-orbitals
isolated ion spherical coordinated octahedral coordinated

ligand field ligand field
Figure 2.7: Ligand field scheme of an octahedral complex.
the axes of coordinates (dxy , dxz , dyz ) is pronounced, while the interaction with the orbitals lying
on the axes (dz2 and dx2 −y2 ) is weaker (see Figure 2.8). With this, the splitting of the orbitals
is inverse to that of an octahedral ligand field. Figure 2.9 illustrates the resulting ligand field.
Again, the dxy , dxz , dyz orbitals (t2 states) and the dz2 and dx2 −y2 (e states) are degenerated.
Because only four ligands interact with the metal center, the ligand field splitting between these
two states is lower as observed for octahedral complexes (6 ligands). The ligand field spliting
energy is approximately ∆t = 4/9|∆O | = 4.45 Dq and splits between the two states in such a way,
that the barycenter of the orbital energies is equal to the energy for a spherically symmetrical
ligand field.
Spin States In some transition metal complexes, the electronic configuration of the transition
metal can basically possess two different spin states for the same oxidation state (i.e. number
of d-electrons): the high-spin and the low-spin configurations. These configurations differ in
the kind of occupation of the different orbitals. On the one hand, it is possible to occupy all
orbitals by unpaired electrons only (high-spin), or by occupying certain orbitals with paired
electrons (low-spin). Because energy has to be spend for pairing electrons, it is a question of
the energy difference between the t2g and the eg state, whether it is energetically more beneficial
to occupy the orbitals with paired or unpaired electrons. For instance, in the case of octahedral
coordination, population of one dxy , dxz , dyz orbital results in a stabilzation by 4 Dq. Addition
of a second electron will gain further 4 Dq and for d3 configuration the stabilization energy is
−12 Dq. For the d4 configuration two cases occur. On the one hand, by population of a further
t2g orbital the stabilization energy would be −16 Dq. But for this, energy is required for spin
11
dxy dxz dyz
z z z
y y y
x x x
dx2 −y2 dz2
z z
= ligand
y y
x x
Figure 2.8: Tetrahedral coordination of d-orbitals.
t2
2/5 ∆t
degenerate d-orbitals
∆t
Energy
3/5 ∆t
d-orbitals
isolated ion spherical coordinated tetrahedral coordinated

ligand field ligand field
Figure 2.9: Ligand field scheme of a tetrahedral complex.
pairing, which reduces the overall energy gain. Therefore, occupation of the eg states may
result in larger energy gains, although the ligand field stabilization energy is only −6 Dq (-12 +
12
te eg
6 Dq.
6 Dq.
Energy
∆O
∆O
4 Dq.
4 Dq.
t2g t2g
d5 low-spin d5 high-spin
Figure 2.10: Low-spin (left) and high-spin configuration (right) of an octahedral complex.
6). Thus, if the ligand field splitting energy (∆ = 10 Dq) exceeds the spin pairing energy, the
formation of low spin complexes is preferred. For an octahedral ligand field, the high-spin and
low-spin configurations are shown for the d5 configuration of a transition metal in Figure 2.10.
These two different spin states exist in the octahedral coordination only for d4 , d5 , d6 , d7 electron
configurations of the transition metal. In d1 - d3 only the low energy orbitals are occupied and
for d8 - d10 the low energy orbitals (t2g orbitals) are always occupied by six electrons. Which
of the two spin state is preferred depends on the ligands and the center metal ion. The absolute
values for the ligand field splitting energy ∆O depends on the nature of the metal center and
the ligands involved. The order of the ligand field splitting energy and with this the preferred
spin state can be derived from the spectrochemical series of the ligands and metals/ions. The
spectrochemical series for the ligands is:
I− <Cl− <F− <OH− <H2 O<NH3 <CN− ≈ CO.
A lower value in this series means a lower ligand field splitting energy (∆ in figure Figure 2.10)
and thus more likely a high-spin complex.
The spectrochemical series for the metal ions is:
Mn2+ <Ni2+ <Co2+ <Fe2+ <V2+ <Fe3+ <Cr3+ <V3+ <Co3+

<Mn4+ <Mo3+ <Rh3+ <Pd4+ <Ir3+ <Re4+ <Pt4+ .
The order of the metal ions follows the same order as for the ligands. A position on the left
equals to a smaller ligand field splitting energy. The 3d-metals are found on the left side, while
the 4d- and 5d-metals are on the right side. As a result, high spin complexes are rarely known
for 4d- and 5d-metal complexes.
The ligand field splitting also depends on the coordination environment. For example the
ligand field splitting in tetrahedral complexes is lower than in octahedral complexes (see section
2.1.4.2). Hence, due to the smaller energy difference between the t2 and the e state, low-spin
complexes are not known for tetrahedral complexes till now.
13
2.1.5 Interaction of Light with Chemical Bonds
2.1.5.1 General Considerations
Absorption of radiation occurs due to interaction of the alternating magnetic or electronic field
with a permanent or induced electric or magnetic dipole in the irradiated medium. If visible or
ultraviolet radiation is considered, interactions with the valence electrons of the species cause
the absorption. Absorption of light excites the valence electrons from the highest occupied
molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO). The electronic
state of the species is changed. In contrast, the absorption of infrared radiation just causes
transitions between different vibrational states in the same electronic state. Within the scope of
this script only ultraviolet and visible irradiation will be considered.
2.1.5.2 Energy of Photons
Electronic transitions between the different orbitals can cause a coloring of chemical substances.
Light in the visible region (400 nm to 800 nm) possesses energies between 300 kJ mol−1 and
120 kJ mol−1 (see section 2.1.2 for details on the calculation). Because electrons are excited to
a higher energy level during absorption of light, the energy difference (∆E) between the two
energy levels has to correspond to the energy of the photons:
∆E = E2 − E1 = hν. (2.6)
The UV region of the electromagnetic spectrum comprises wavelengths between 200 nm and
400 nm. That equals an energy of 600 kJ mol−1 to 300 kJ mol−1 . With this, photons in the UV and
visible region (200 nm to 800 nm) have an energy of 600 kJ mol−1 to 120 kJ mol−1 . Hence, the
energy of photons can be larger than the enthalpies of single-bonds. For example, the enthalpy of
the C – H bond equals to 413 kJ mol−1 and the enthalpy of the C – Cl bond equals to 339 kJ mol−1 .
2.1.5.3 F RANCK -C ONDON Principle
Changing the electronic state of a molecule results in a change of the forces between the atomic
nuclei. This can lead even to the dissociation of molecules and/or the initiation of chemical
reactions. Since the nuclei are much heavier than the electrons, a change of the electronic state
happens so fast that the nuclei have no time to respond to this new situation. This means that
the distribution of the electron density within the molecule is changed causing vibrations of
the nuclei. Because the structure of the nuclei does not change during the electronic transition,
the transition is vertical. This concept is called the F RANCK -C ONDON principle. The most
intense transition occurs from the vibrational ground state of the electronic ground state to that
14
S1 LUMO
E
HOMO
S0 LUMO
SR HOMO
A F
hν hν F
R0 R1 RX-Y
Figure 2.11: Scheme of the electronic states S0 and S1 as potential curves and the transitions of
a light-induced excitation and a following relaxation of an electron.
vibrational state of the excited electronic state for which the overlap of the probability functions
has its maximum. According to K ASHA’s rule, the electron will relax quickly to the vibrational
ground state of the electronic excited state. From this level it can decay to the electronic ground
state. This can be associated by a photon emission (fluorescence). Again, the electron will not
decay to the lowest vibrational level of the electronic ground state, but to that vibrational level,
where the overlap of the wave functions is largest. Figure 2.11 illustrates the processes.
The energy required to excite an electron depends on the energy difference between the two
electronic levels, between which the electron changes. This difference depends on the chemical
nature of the molecule. Typical examples of electronic transitions are π → π ∗ transitions occur-
ring when a C – C double bond absorbs light. In this case, the electron is excited from a π orbital
to an antibonding π ∗ orbital. For an isolated double bond an energy of about 7 eV is required,
corresponding to a wavelength of 180 nm. The required energy changes if the electronic system
is changed, e.g. by a second conjugated double bond or an aromatic ring. In these cases, the
energy between the electronic levels decreases and with this the required energy for the transi-
tion. Due to the vibrational relaxations, the energy is lower and accordingly the wavelength of
the photons is larger for fluorescence as for absorption. A more detailed description of these
processes can be found in textbooks on physical chemistry or quantum mechanics.
15
2.1.5.4 J ABLONSKI Diagram
Processes associated with electronic excited states can be visualized with the so called JABLON -
SKI diagram. It uses the F RANCK -C ONDON principle and relinquishes the visualization of the
nuclei distance. Only electronic transitions and vibrational levels are included. This enables the
inclusion of additional information on the electronic processes. The most prominent electronic
transitions are illustrated in Figure 2.12:
• Absorption of light (A): An electron is excited from the ground state to an excited state.
• Fluoreszence (F): Transition of an electron from the excited singlet state to the ground
state during which light is emitted.
• Phosphoreszence (P): Transition of an electron from the excited triplet state to the ground
state during which light is emitted.
• Vibrational relaxation (SR): An electron relaxes from an excited vibrational level to the
lowest vibrational level without emitting light.
• Internal Conversion (IC): Nonradiative transition of an electron between electronic states
of similar spin multiplicity.
• Intersystem Crossing (ISC): Nonradiative transition of an electron between electronic
states of different spin multiplicity.
2.1.5.5 Charge-Transfer
The large energy of photons can induce different electronic excitations in metal complexes. The
decreasing transmission at a certain wavelength can be observed as the color of the complexes.
Many pigments used industrially are colored due to charge-transfer transitions. In metal com-
plexes, four different electronic transitions can be distinguished:
• metal charge transfer (MC),
• metal to ligand charge transfer (MLCT),
• ligand to metal charge transfer (LMCT) and
• ligand to ligand charge transfer (LC).
The schematic representation is shown in Figure 2.13. The metal charge transfer (MC) is an
electronic transition between the d-orbitals of the metal ion. Low energy MCs can be expected
for the 3rd period transitions metals. The metal to ligand charge transfer (MLCT) is the transition
of an electron from an orbital of the metal ion to an orbital of the ligand, more precisely for
Figure 2.13 from a d-orbital of the metal ion towards the π ∗ -orbital of the ligand. MLCT-
transitions are to be expected, when the metal is easy to oxidize and the ligand is easy to reduce.
The ligand to metal charge transfer (LMCT) is the equivalent transfer of an electron from the
ligand π-orbital towards the d-orbital of the metal. LMCTs can be expected when the metal is
16
E
π *2
π *1
SR
S2 IC
n,π
SR
π *2
π *1
ISC
S1 104 – 1012 s-1 π *2
n,π
IC π *1
SR
1012 s-1 T1
n,π
SR A F ISC
≤ 1012 s-1 1015 – 1016 s-1 106 – 109 s-1 10-1 – 105 s-1
P
102 – 104 s-1
π *2
π *1
n,π
ground state S0
Figure 2.12: JABLONSKI diagram of an organic molecule with activation and deactivation pro-
cesses and their rate constants. Radiative transitions are indicated by straight ,
vibrational relaxations by squiggly and transitions between different electronic
states by dashed arrows .
easy to reduce and the ligand is easy to oxidize. The ligand to ligand charge transfer (LC or
LLCT) is the transition from a π-orbital of a ligand towards the π ∗ -orbital of the ligand. LCs
usually occur in aromatic systems with an extended π-system.
2.1.6 Relations Between Chemical Structure and Electron Spectra
Absorption of light, or more general electromagnetic irradiation, strongly depends on the chem-
ical composition of the molecule. The two functionalities of a chemical substance that sig-
nificantly influence the nature of a molecule’s absorption spectrum are functional groups and
conjugated π-systems. For both elements absorption of light corresponds to a transition of an
electron from an n-, σ - or π-orbital to a σ ∗ - or π ∗ -orbital. For light absorption in the UV-Vis-
range following electron transitions are possible: n → π ∗ , n → σ ∗ , σ → σ ∗ , π → π ∗ .[14,15]
n → σ ∗ transitions usually occur in saturated molecules containing heteroatoms such as O,
N and S. In this case, electrons of heteroatom’s lone pairs are excited to the σ ∗ -orbital which
can already be observed at wavelengths λ >200 nm. Such compounds are usually used as sol-
17
σ ∗M MLCT LC
4p
π ∗L π∗
Energy
4s
σ ∗M MC LMCT
3d π ∗M
πL π
σL σ
metal orbital molecular orbital ligand orbital
Figure 2.13: Possible charge transfer transitions shown for an octahedral 3d-complex as an
example.
vents. Common examples are water, ethanol, chloroform, short chained ethers (diethylether)
and amines (methylamine).[14]
n → π ∗ transitions can be observed in unsaturated molecules comprising heteroatoms. For
these transitions electrons, which are located in the heteroatom’s n-orbitals, are excited to the
anti-bonding orbital of a π-bond. Important examples possessing n → π ∗ transitions are alde-
hydes and ketones. For saturated aldehydes and ketones n → π ∗ transitions can be observed at
wavelengths of λ = 270 nm to 300 nm. For unsaturated carbonyl compounds with π-bonds at α
and β position such transitions occur at wavelengths of λ = 300 nm to 350 nm.[14]
For σ → σ ∗ transitions higher excitation energies are required. For saturated hydrocarbons
these are the only observed transitions. Thereby σ → σ ∗ transitions of C – H bondings are
excited more easily than σ → σ ∗ of C – C-bondings due to small differences in the bond energy.
These transitions occur in a wavelength region of 100 nm to 200 nm.[14]
π → π ∗ transitions can be observed for every molecule that contains a π-bonding system or π-
electrons (e.g. chromophores, polyenes, etc.). During this transition electrons from the π-orbital
are raised to a anti-bonding π ∗ -orbital. A crucial parameter for the amount of energy required
18
for excitation is the extent of the conjugated π-system. In order to induce π → π ∗ transitions
in ethylene, possessing an isolated π-bonding, a wavelength of λ = 193 nm is needed due to
a high energy difference between HOMO and LUMO. Because the energy difference between
the HOMO and LUMO depends on the number of conjugated π-bondings, light with longer
wavelengths can induce π → π ∗ transitions in conjugated π-systems.[14,15]
As a consequence of the tuneability of the energy difference between the HOMO and LUMO,
linear or cyclic conjugated π-systems are often used as basic chromophores. Chromophoric
groups absorb light in the UV-VIS range and are therefore essential for the functionality of a
molecule e.g. as a dye. When the extent of a π-system exceeds a certain value, absorption of
light in the visible range is observed. In addition to a chromophoric backbone, the addition of
auxochromic groups to the molecule can affect the absorption spectrum of the molecule. Aux-
ochromic substituents contain heteroatoms. Examples are – OR, – NR2 , – SR moieties which
could behave as an +M donor. These substituents lead to a shift of the absorption maximum to
higher wavelengths (bathochromic effect) and an increase of the molar extinction coefficient and
with that the absorption (hyperchromic effect).[15]
Antiauxochromic groups show enhanced bathochromic and hyperchromic effects by extend-
ing the conjugated π-system. These substituentes (e.g. – NO2 , – CN, – CO) behave as -M or -I
acceptors, respectively.[15]
The counterpart to auxochromic substituents are hypsochromic groups. These groups are ster-
ically demanding and voluminous. Addition of such substituents to a chromophoric backbone
leads to a twist of the molecule and with that to an interruption of the conjugated π-system. This
leads to a shift of the absorption to shorter wavelengths (hypsochromic effect) and often to a
decrease of the absorption band intensity (hypochromic effect).[14,15]
Azobenzene is an outstanding example to highlight the dependence of the absorption on pos-
sible substituents as well as on the configuration (see Figure 2.14). (E)-azobenzene contains
a weaker absorption band of a n → π ∗ transition at 450 nm and a stronger absorption band of
a π → π ∗ transition at 330 nm. Isomerization to (Z)-azobenzene results in a blue shift of the
π → π ∗ band due to twisting of the molecule. Adding of auxochromic (+M-Donors) and/or
antiauxochromic substitutents leads to a red shift and higher absorption intensities (see above).
2.1.7 W OODWARD -H OFFMANN Rules
The Woodward-Hoffmann rules, are a set of rules in organic chemistry that predict the bar-
rier heights of pericyclic reactions based on the conservation of orbital symmetry. The the-
ory was devised by Robert Burns Woodward and Roald Hoffmann in 1969. Roald Hoffmann
was awarded the Nobel prize in chemistry in 1981. The Woodward-Hoffmann rules provide an
19
N N
N N N N
N N N N
N
O O
n � �� n � �� n � �� n � ��
��= 450 nm ��= 430 nm ��= 463 nm ��= 478 nm
��= 46 � ��= 150 � ��= 2750 ��= 3310
�3 �� 0 �� 0 0
��= 450 nm ��= 280 nm
��= 1700 ��= 510
0 0
Figure 2.14: Influence of different configurations and substituents on absorption behaviour of

azobenzene.
Figure 2.15: Parallel approach of two ethylene molecules and energy levels of the orbitals.[16]
approach to explain differences between thermal and photochemical electrocyclic reactions by

considering the orbital symmetry. These rules can be applied to concerted reactions involving π-
orbitals, electrocyclic reactions, cycloadditions, sigmatropic and group transfer reactions. They
can not be applied to reactions proceeding through a radical mechanism and reactive intermedi-
ates. Concerted reactions involving π orbitals take place readily when the orbital symmetry is
maintained during the reaction process. With this, "Orbital symmetry is conserved in concerted
reactions".[16]
Figure 2.15 shows the parallel approach of two ehtlyene maximal symmetric oriented molecules
with four π orbitals during reaction. The four π orbitals will be transformed into four σ orbitals
20
Figure 2.16: Complete correlation diagram for the formation of cyclobutane from two
molecules of ethylene.[16]
of cyclobutane. In the reaction of two ethylene molecules three mirror planes 1, 2 and 3 exist for
the initial and final states (see Figure 2.15). In the correlation diagram π orbitals, symmetric to
mirror planes 1 and 2, are noted by SS. Orbitals, that are antisymmetric to the mirror planes, are
abbreviated as AA and orbitals, that are symmetric to mirror plane 1 but antisymmetric to mirror
plane 2, are noted as SA and vice versa (see Figures 2.16 and 2.15). The symmetry behavior for
symmetry-oriented orbital correlation diagrams for the initial state and final state as well as the
symmetry behavior for mirror planes 1 and 2 are shown in Figure 2.16.
The reaction is impossible from the two ground-state ethylene molecules in a concerted re-
action while maintaining the orbital symmetry. Hence, the reaction can only take place to give
ground-state cyclobutane through a transition state by activation of the molecules. The required
energy corresponds to the activation energy. Photochemical excitation of an electron from a π
orbital to the lowest anti-bonding orbital leads to a more favorable overall energy balance. Re-
actions of the ground state are forbidden by symmetry. Despite this, reactions of the excited
state are symmetry allowed. With these considerations, the [2+2]-cycloadditions are thermally
prohibited and photochemically allowed (allowed in excited state), [4+2]-cycloadditions (Diels-
Alder-Reaction) are thermally allowed and photochemically prohibited (allowed in ground state).
The general rules for this type of reaction can be derived from the number of π orbitals involved
in the reaction. The number of π orbitals are given as m and n. The selection rules for [m+n]
cycloadditions are shown in Table 2.2. In the table, the subscripts “s” and “a” represent suprafa-
cial and antrafacial describe the geometrical orientations of formed or broken bonds during the
21
Table 2.2: Selection rules for [m+n] cycloadditions. m and n represent the number of electrons
involved in the respective molecules. q is an integer.[16]
Allowed in ground state Allowed in excited state
m+n
Forbidden in excited state Forbidden in ground state
4q ms +na ms +ns
4q ma +ns ma +na
4q+2 ms +ns ms +na
4q+2 ma +na ma +ns
Figure 2.17: Orientations of suprafacial and antrafacial processes.[16]
reaction. A suprafacail process is a process where the changing bonds lie on the same face. Con-
sequently, for antrafacial the formed or broken bonds lie on different faces (see Figure 2.17).
22
2.2 Reaction Types
Figure 2.18: Reaction of 1,3-Butadiene with ethylen.[16]
2.2 Reaction Types
2.2.1 Cycloadditions
2.2.1.1 General Concept
Cycloadditions allow the synthesis of cyclic compounds from typically alkenes in a concerted
reaction step. According to the W OODWARD -H OFFMANN rules the possibilities of formation
of cyclic compounds depend on the symmetry of the orbitals of the reactants. The reaction
of reactants with n and m π-electrons can be initiated either thermally or photochemically.[16]
Such cycloadditions can be classified by the following scheme: [mπ+nπ]. Reactant A possesses
mπ-electrons and reactant B nπ-electrons. Reactions between reactants of the [2·nπ+nπ] type
proceed thermally, while reactions of the [nπ+nπ] must be intitiated photochemically. Besides
alkenes, π-bonds of heteroatoms can follow this reaction path as well. To illustrated the synthetic
potential, [4+2]-cycloadditions and [2+2]-cycloadditions are introduced below.[16,17]
2.2.1.2 [4+2]-Cycloadditions (D IELS -A LDER-Reactions)
[4+2]-cycloadditions (D IELS -A LDER-reactions) represent the prototype of cycloadditions of the

[2·nπ+nπ] type. In this kind of reactions, a molecule with 2·nπ electrons (e.g. diene) reacts with
a molecule with nπ electrons (e.g. dienophile) to a new cyclic product. The [4+2]-cycloaddition
of butadiene with ethylene and the correlation diagram of molecule orbitals. In this case, each
bonding level of the reactants correlates with a product bonding level and the ground state lev-
els correlate directly. Therewith, there is no or only a low activation energy required for this
thermally allowed process.
The reactions in which the electrons shift in a concerted step and form a cyclic ring are
called an electrocyclic reactions or cycloadditions. The Diels-Alder reaction is special for [4+2]-
cycloadditions. In this reaction, the conjugated π-system (diene) provides four π-electrons to
the reaction and the other partner (dieneophile) provides two electrons. The reaction and elec-
tron flow is shown in Figure 2.18.[18] The cycloaddition reactions are stereospecific because of
the concerted reaction mechanism. That means, the final structure of product dependents on
the structure of the reactants (see Figure 2.19). The reactivity of compounds depends on sub-
stituents. Donor substituents increase the energy of HOMO and LUMO, acceptor substituents
23
2.2 Reaction Types
COOCH3 COOCH3
COOCH3 COOCH3
COOCH3 COOCH3
COOCH3 COOCH3
Figure 2.19: Reaction of 1,3-Butadiene with maleic acid dimethyl ester.[18]
O h� O
O O
Figure 2.20: General reaction mechanism of Paternò-Büchi reaction.
decrease the energy of both orbitals. The presence of electron attracting substituent increase
and electron donating substituents decrease the reactivity of an alkene. For dienes the situa-
tion is inverse, the reactivity increases with electron-rich substituents like carbonyl containing
groups. Therewith, high reaction rates are observed for electron-rich dienes with electron-poor
dienophiles.[19]
2.2.1.3 [2+2]-Cycloadditions
[2+2]-cycloadditions give access to four membered rings starting from two alkenes or one alkene
and a carbonyl compound. The symmetry of the π orbitals prohibits thermally initiated cycload-
ditions, but the photochemically initiated pathway is permitted. This applies for all [nπ+nπ]
reactions. Irradiation with light of appropriated wavelength excites one reactant to the LUMO
level. This level possesses the correct orbital symmetry and allows the concerted reaction. Fig-
ure 2.15 shows the correlation diagram for the reaction of two ethene molecules.[16]
An important example of [2+2]-cycloaddition reactions is the PATERNÒ -B ÜCHI reaction, in
which a carbonyl group reacts with an alkene and forms an oxetane. This reaction is allowed
only photochemically and thermally prohibited. The general procedure and reaction mechanism
of PATERNÒ -B ÜCHI reaction is shown in Figure 2.20. In most cases the reaction proceeds via a
1,4-biradical and regioisomerism is determined by the stability of the biradical. Hence, orbital
symmetry is not necessarily maintained.
24
2.2 Reaction Types
H3C CH3 H3C CH3
O
+ 1
O2
O
CH3 CH3
(a) (b)
Figure 2.21: (a) Reaction scheme for the synthesis of ascaridole from α-terpinene and 1O2 . (b)
Production site for ascaridole by solar irradiation.[21]
2.2.2 Photooxygenations and S CHENCK-En-Reactions
Photosensitizers can be used to introduce oxygen into organic compounds. One of the best
investigated reactions of this type is the synthesis of ascaridole starting from α-terpinene and
singlet oxygen (see Figure 2.21a). The synthesis was described first by S CHENCK et al.[20,21]
One of the first production sites for ascaridole is shown in Figure 2.21b. Eosin was added
to an alcoholic solution of α-terpinene and irradiated in the presence of oxygen. After work
up ascaridole could be isolated and characterized. S CHENCK et al. generalized the results and
pointed out, that 1,3-dienes react with oxygen to yield an endoperoxide when a photosensitizer
is used. This could be proven by transfering the reaction concept to other diene-systems, e.g. α-
phellandrene and 1,3-cyclohexadiene, which also resulted in the formation of endoperoxides.[22]
By irradiating the sensitizer with light of appropriate wavelength, excitation from the elec-
tronic ground state to the first excited electronic state S1 occurs. Subsequently, the sensitizer
undergoes intersystem crossing and transitions to the first triplet state. Due to the relatively long
lifetime of this electronic state, it is possible that the sensitizer in the triplet state interacts with
a molecule of dissolved oxygen, which is in the triplet state as well. The sensitizer molecule
returns to the electronic ground state, while the oxygen molecule changes into the first excited
electronic state. For a oxygen molecule this is the first singlet state. The singlet oxygen ( 1O2 )
is able to react with suitable organic reactants.[23–27] The lifetime of 1O2 in the liquid phase is a
crucial parameter for the efficiency of the photooxygenation because this excited state will fall
back to the more stable 3O2 . The lifetime of 1O2 is influenced significantly by the solvent. In
aprotic solvents such as tetrachloromethane the lifetime can reach values of up to 30 ms, while
the lifetime in polar and/or protic solvents is much shorter. For example, the lifetime in methanol
is just 10 µs. When the reactivity of the organic substrate is low, a short lifetime of 1O2 will ad-
25
2.2 Reaction Types
R R O O
(a) + O O R R
R R R R
O OH
H
R
(b) R R R
R
R
R + O O
R R
R
R R R
R R
R O
(c)
R + O O
O
R R
R R R
Figure 2.22: Possible reaction pathways of 1O2 with organic substances. (a) Formation of 1,2-
Dioxetanes, (b) S CHENCK-En-Reaction, (c) [4+2] D IELS -A LDER-Reaction.
ditionally slow down the overall reaction rate because the probability of collisions between the
organic substrate and activated oxygen decreases. Hence, the choice of the solvent is crucial for
photooxygenations.
Many 1,3-dienes are known, which undergo photooxygenation to form the corresponding
endoperoxide via the [4+2] D IELS -A LDER-reaction. Besides forming endoperoxides, singlet
oxygen can also react differently. Alkenes with an α-hydrogen atom form hydroperoxides via
the S CHENK-En-reaction.[28] Simple alkenes without an α-hydrogen atom can react with 1O2
to form 1,2-dioxetanes through a [2+2]-cycloaddition. These three reaction types are shown in
Figure 2.22.
Different dyes can be used as sensitizers. Popular examples are methylene blue, rose bengal
and tetraphenylporphyrin (see Figure 2.23).[29] The choice of the sensitizer is mainly influenced
by the available light source and the solvent chosen.
Singlet oxygen can be generated through thermal reactions as well. In most cases, hydrogen
peroxide is used with several additives such as molybdates or hypochlorite.
H2 O2 + ClO− −−→ H2 O + Cl− + 1O2 , (2.7)

MoO2−
2 H2 O2 −−−−→ 2 H2 O + 1O2 .
4
(2.8)
Because only the path of generation changes, but not the reactants, the product spectrum, which
can be accessed, is similar to that of the photosensitized reactions.[30–32] Although the design of
the reactors for the thermal generation of singlet oxygen is easier, these methods have issues with
the high oxidation potential of e.g. hypochlorite or hydrogen peroxide.[33] The presence of such
26
2.2 Reaction Types
I I
+ -
Na O O O
+
I I N S N
- +
Cl COO Na
N
Cl Cl
Cl
Bengalrosa Methylen Blau
NH HN
Tetraphenylporphyrin
Figure 2.23: Chemical structures of selected photosensitizers.
oxidative reactants can lead to unwanted side reactions. When H2 O2 is used as oxygen source
together with MoO24 – , the generation of 1O2 only proceeds efficiently in water and aqueous
solutions of methanol or ethanol.[34] Hence, reactions with hydrophobic substrates are difficult.
A possible solution is the use of biphasic systems, especially microemulsions.[35,36]
Endoperoxides are of high interest from a pharmaceutical point of view because several
anticancer- and antimalaria-drugs are organic peroxides.[37,38] With this, efficient access to or-
ganic peroxides is very desirable.
Several scientific publications deal with photooxygenations in microstructured photoreactors
to develop efficient processes for the production of organic peroxides. First studies focused on
the feasibility of gas-liquid for the reactions in this reactor type.[39,40] More recent publications
also addressed the reactor concepts for contacting a gas with a liquid phase and the required
dimensions of the reactor.[41,42] It was also shown, that it is possible to set up photochemical
processes with microstructured reactors, which show an improved productivity compared to
conventional photoreactors.[43] Such a setup can also be used to synthesize the antimalaria-drug
Artemisinin.[44]
27
2.2 Reaction Types
A B C A B C
Figure 2.24: Scheme of a photolysis reaction.
O h� O
Figure 2.25: Excitation of an ketone and formation of the biradical.
R R' h� R
R'
O O
Figure 2.26: Norrish type I reaction.
2.2.3 N ORRISH Type I and Type II Reactions
Norrish type reactions are a member of photolysis reactions. In general photolysis implies the
homolytic σ -bond cleavage by the absorption of electromagnetic irradiation usually in the UV-
range. When there is no additional support structure, this process results in molecular fragmen-
tation. In Figure 2.24 the general scheme of a photolysis reaction is depicted.[45]
A common photolysis reaction is the photoinduced cleavage of isoelectronic CO and N2 from
carbonyl and azo compounds.[15] In chemical substances containing carbonyl and azo function-
alities, absorption of light with a wavelength of λ = 230 nm to 330 nm usually initiates a n→π ∗
excitation. By entering the triplet state via intersystem crossing (ISC), those functional groups
possess biradical characteristics (see Figure 2.25).[15,46]
From this state, several competitive, consecutive reactions can occur such as radical recombi-
nation, α-bond cleavages, intra- and intermolecular H-abstractions as well as the formation of a
cycloadduct via addition to a C – C-double. The Norrish type I cleavage is a α-cleavage of an ad-
jacent C – C σ -bond, yielding a set of fragmentation products. Norrish type II cleavage involves
the abstraction of a γ-H atom, finally resulting in an enol and an alkene or cyclization.[14]
2.2.3.1 Norrish Type I Reactions
An example of the Norrish type I reaction is depicted in Figure 2.26. Norrish type I reactions
usually occur for carbonyl compounds (ketones, aldehydes) under irradiation with light of a
wavelength of λ = 230 nm to 330 nm in a non-reactive solvent. During the first reaction step,
an α-bond cleavage, one acyl and one alkyl radical are generated. Due to movements of both
radicals in the solvent cage by diffusion and rotation, three consecutive reactions are possible.[47]
28
2.2 Reaction Types
Figure 2.27: Possible consecutive reaction pathways for a Norrish type I reaction.
Firstly, CO can be released from the acyl radical (decarbonylation, see also section 2.2.10). Dur-
ing this process alkyl radicals are formed, that can be recombined or stabilized via disproportion.
This typically results in the formation of alkanes and alkenes. Secondly, by leaving the solvent
cage a H-atom can be abstracted by the acyl radical yielding an alkene and an aldehyde. Thirdly,
by presence of an α-H in the acyl radical, ketene formation by H-abstraction can occur (see Fig-
ure 2.27). Additionally, a back reaction to the reactant through recombination is also possible
inside the solvent cage. On this account, the quantum yield of the products for Norrish type I
reactions is usually significantly below 1.[14,47]
The Norrish type I reaction can be influenced via three different parameters. One crucial pa-
rameter is the excitation level. It is assumed that the α-bond cleavage proceeds 100 to 1000
times faster from the nπ ∗ -excitation state than from a ππ ∗ state. The multiplicity of the excited
state constitutes an additional important parameter. The reaction can occur 100 times faster
from a nπ ∗ triplet state than from a nπ ∗ singlet state. For aromatic ketones or aldehydes fast
intersystem crossing rates are observed (> 108 s−1 ). For these substances reactions occur exclu-
sively from triplet state. Aliphatic ketones and aldehydes show much lower ISC rates. For these
29
2.2 Reaction Types
O
O
hv hv
O
77 K 8K O
O
Figure 2.28: Synthesis of anti aromatic cyclobutadiene.
substrates, the Norrish type I reaction could occur from singlet and triplet state. Finally, the pos-
sible substituents and molecular structures strongly affect the secondary reaction pathways. The
first reaction step (α-bond cleavage) as well as the decarbonylation, that corresponds to the first
consecutive reaction pathway, can be favored by formation of stabilized radicals such as benzyl-
or t-alkylradicals. Furthermore, sterical issues have to be considered. The reaction rate for the
α-bond cleavage step increases when it is possible to reduce sterical tension through radical for-
mation. On this account, the cleavage rate increases via cyclohexanones to cyclopentanones and
cyclobutanones. In a non-symmetrically substituted ketone usually the weakest C – C-σ -bond is
broken, yielding the radical with the highest possible number of substituents.[14,15]
The Norrish type I reaction is a fundamental member of photoreactions in synthetic organic
chemistry. One outstanding example for this reaction type is the photochemical formation of
the unstable antiaromatic cyclobutadiene, which could be synthesized by additional use of low
temperature techniques (see Figure 2.28).[14]
Another great example is the synthesis of tetrahedrane system demonstrating high intramolec-
ular tension. Through irradiation of t-butyl-cyclopentadienone the desired tetra-t-butyl-tetrahedran
was obtained through decarbonylation. t-butyl groups were used for stabilization.[14]
2.2.3.2 Norrish Type II Reactions
Norrish type II reactions are characterized by formation of a biradical through intramolecu-

lar γ-H-abstraction (see Figure 2.29). In the course of this a 6-ring-transition state is formed.
Through dissociation of the α − β -positioned bond (referenced to the carbonyl group) the bi-
radical turns into an olefine and an enole. Both products can be considered as coupled main
products of the ketone fragmentation. In lower amounts (10 % to 25 %) cyclobutanole is formed
as a recombination product. This process is known as the Yang-cyclization. Depending on the
α substituent, the cyclization product fraction can raise up to 90 %. This can occur for example
for α, α-dimethyl-butyrophenone. The back reaction through H transfer is also possible. By
this, the educt ketone is released, which corresponds formally to a deactivation of the excited
state. Because biradical formation is exothermic, the amount of energy released is high enough
to initiate the back reaction. That is why the back reaction has always to be taken into account.
30
2.2 Reaction Types
R1 R1 R1
O h� O O
H H H
R2 R2 R2
R3 R3 R3
R1 R1
R3 R1 +
2
R OH R2 R3 OH O
Figure 2.29: Norrish type II reaction mechanism.
Laserphotolysis experiments showed that the lifetime of biradicals is in the range of 30 ns

to 100 ns. The lifetime can be influenced by the polarity of the solvent cage. Higher lifetime
are observed in alcohols or aqueous acetonitrile. This is due to hydrogen bond formation with
solvent cage molecules. Lower values were observed in non polar solvents.[14,15]
2.2.3.3 Norrish Type I Reactions vs. Norrish Type II Reactions
The occurring cleavage type during irradiation of a ketone strongly depends on the substrates
structure and the biradical stability. Lower aliphatic ketones without any γ − H-atoms as well
as cyclic ketones undergo Norrish type I reactions. As an exceptional case, tert-butylketones
undergo Norrish type I reactions despite of the existing γ − H-atoms. This is due to the high
stability of intermediate tert-butylradicals.
Norrish type II reactions are observed for aliphatic ketones and higher alkyl phenyl ketones
containing γ −H-atoms. Lower alkyl phenyl ketones react to pinacoles via external H-abstraction.
This also applies for diaryl ketones, which can not be dissociated photochemically.[14]
2.2.4 BARTON Reaction
This photochemical reaction was demonstrated first by D. H. R. BARTON in 1960. In a narrow

sense, the BARTON reaction is the photolysis of an alkyl nitrite to form a δ -nitroso alcohol.[48]
The alkyl nitrite can be formed from a hydroxy group by reaction with NOCl or nitrosyl hydride.
After the actual BARTON reaction, the nitroso alcohol can be dehydrated to a carbonyl group.
The mechanism is shown in Figure 2.30.
The photochemical RO – NO cleavage yields a nitrosy radical and an alkoxide radical. Within
a six-membered transition state, the alkoxide radical abstracts the δ -hydrogen. After free radi-
31
2.2 Reaction Types
Figure 2.30: Reaction mechanism of the BARTON reaction with preceding akyl nitite formation
and consecutive hydrolysis.
Figure 2.31: Reaction scheme of the synthesis of aldosterone acetate.
cal recombination of nitrogen mono oxide and the alkyl radical, the resulting nitroso compound
undergoes tautomerization to give a δ -nitroso alcohol.[49] The formation of aldosterone acetate
oxime demonstrated by BARTON et. al is an example for the application of this sythesis. Fig-
ure 2.31 shows the reaction scheme. The nitrite can be obtained by adding nitrosyl chloride
and consecutive irradiation for 75 min under nitrogen with a 200 W Hg lamp. The oxime is
received by treatment with a 5 % sodium nitrite solution. By hydrolysis the hemiacetal can be
obtained.[50]
2.2.5 Photolysis of Azido Compounds
Organic compounds containing a functional N3 -group are called azides. In inorganic chemistry
azides are the salts of hydrazoic acid. Depending on the counter ion, azides can have a propensity
to explode. Driving force for this degradation is the release of nitrogen. On this account, heavy
32
2.2 Reaction Types
metal azides such as Pb(N3 )2 are used as primary explosives. This also applies for most organic
azides. Nevertheless, organic azides are important intermediates in synthetic organic chemistry
for heterocycles such as triazoles or tetrazoles. This is also the reason for the interest of chemical
industry in this kind of substances.[51,52]
The N3 group is linear, forming polar mesomeric structures. Additionally, it can be stabilized
by conjugation with adjacent aromatic systems. The polar mesomeric structure implies the reac-
tion behavior of azides as 1,3 bipole as well as the regioselectivity in reactions with nucleophiles
or electrophiles (see Equation 2.9).[51]
⊕ ⊕ ⊕
R N N N R N N N R N N N R N N N (2.9)
Besides conventional organic reactions such as Schmidt and Curtius reactions, azides can
undergo photochemical degradation. This process is called photolysis. By absorption of UV-
light azides decompose by releasing N2 , finally forming nitrenes (see Equation 2.10). Alkyl
azides absorb in the range of 260 nm to 290 nm and aryl azides in the range of 300 nm to 400
nm. On account of this, azides are usually used as precursors for nitrenes in synthethic organic
chemistry.[51]
⊕ hv
R N N N GGGGGGA R N (2.10)
– N2
Nitrenes are analogues of carbenes with only 6 electrons in the outer orbitals. Despite this,
their properties differ from their carbon analogues. Nitrenes are uncharged, high reactive inter-
mediates. Nitrenes stabilize themselves through inter- and intramolecular H-abstraction, [1,2]-
shift, addition or coupling reactions. Nitrene chemistry is therefore an own field of research
that contains reactions from cycloadditions to rearrangements. A distinction is made between
singlet and triplet nitrenes (Equation 2.11).[14] Usually singlet nitrenes are not observed. Triplet
nitrenes are more stable and considered to be the ground state.
R N ↑↓ R N ↑↑ (2.11)
A direct photolysis of most azides leads to imine formation. Characteristic nitrene reaction
products are usually not observed. On this account it is assumed that a [1,2]-rearrangement
occurs simultaneously to N2 abstraction. The quantum yield of alky azide photo reactions is
33
2.2 Reaction Types
hv N
+ + +
N N
N3 N
Figure 2.32: Reaction products of 1-azidonorbornane upon irradiation.
usually above 1. This results from the radical chain reactions that can occur.[14]
hv
PhN3 GGGGGGA N2 + PhN (2.12)
PhN + PhN3 GGGGGGA N2 + 2 PhN (2.13)
2 PhN GGGGGGA Ph−N−N−Ph (2.14)
This way, even high reactive compounds, which could not be synthesized conventionally, are
accessible (for an example see Figure 2.32).[47]
Despite the mentioned differences, many carbene reactions can be transferred to nitrenes.
Similar to carbenes, most nitrene reactions strongly depend on the spin state. Singlet nitrenes
undergo stereospecific additions with olefins, [1,2]-rearrangements as well as insertions into
σ -bonds. Triplet nitrenes add in a non-stereospecific way to double bonds. They undergo H-
abstractions as well as additions to radicals.[47]
Direct photolysis leads to singlet nitrenes first, which then change into to the more stable
triplet nitrene through inter system crossing. By triplet sensitization triplet nitrenes are accessi-
ble directly.[47]
2.2.6 Photonitrosylation
Introduction of heteroatoms is of great synthetic interest. A photochemical reaction type pro-

viding this possibility is the photonitrosylation to build up nitroso functionalities in organic
compounds. Under suited reaction conditions, the nitroso moiety can isomerize to yield an
oxime. A typical reaction procedure is the irradiation of a mixture of the organic reactant with
NOCl, yielding the nitrosylated product and HCl. The presence of HCl leads to isomerization
and formation of the oxime:[53]
R hν R
CH2 + NOCl C N OH, HCl (2.15)
R R
34
2.2 Reaction Types
This reaction path is of great interest for chemical industries, because oximes can be further
converted to lactams, which are important intermediates. Consequently, photooximations were
realized on an industrial scale. An outstanding example of photooximations, that found extended
industrial use, is the photooximation of alkyl compounds. The photochemical ε-caprolactam
synthesis, a precursor to Nylon 6, using cyclohexane and nitrosyl chloride is one of the most
popular examples of this reaction type. This process is conducted in Japan since the 1950s.[24]
With this reaction type the photochemical synthesis of lauryllactam is possible as well, which
is a precursor to Nylon 12. Other examples for photonitrosylations include the use of diverse
aromatic hydrocarbons (e.g. side chain nitrosylation), paraffins or polymers. Furthermore, it is
possible to use other nitrosylations agents such as tert-butyl nitrite or sodium nitrite.[24]
Two mechanisms are discussed for the photonitrosylation. First, a radical mechanism, initi-
ated by homolytic dissociation of NOCl, and secondly a mechanism involving a pre-dissociated
excited state of nitrosyl chloride. Both mechanisms were found to occur in parallel. Depending
on the reaction conditions and most importantly the wavelength of irradiation either the one or
the other mechanism is favored.[24,54]
For the radical reaction pathway, the first step is the homolytic cleavage of nitrosyl chloride.
After that a H-abstraction by the chlorine atom is provoked. The formed alkyl radical sub-
sequently combines with the nitrosyl radical. Due to HCl formation during H-abstraction the
nitrosylated compound can isomerize to an alkanoneoxime.[24,55]
hν
NOCl −−→ NO• + Cl• (2.16)
• •
R2 CH2 + Cl −−→ R2 CH + HCl (2.17)
R2 CH• + NO• −−→ R2 CH−NO (2.18)
R2 CH−NO + HCl −−→ R2 C−N−OH, HCl (2.19)
The mechanism involving a pre-dissociated excited state of nitrosyl chloride occurs mainly when
NOCl is irradiated by light of a wavelength larger than 500 nm. Interaction of the excited NOCl
leads to H-abstraction instead of an interaction with a chlorine radical:[24,54]
h ν> 500 nm
NOCl −−−−−−→ NOCl∗ (2.20)
R2 CH2 + NOCl∗ −−→ R2 CH• + NO• + HCl (2.21)
The following reaction steps are similar to that discussed for the radical mechanism. As a con-
sequence of these two mechanisms, reaction control is important to gain high selectivities and
yields.
For industry the costs of the process are the most relevant parameter. On this account, the
35
2.2 Reaction Types
OH
N H
NOCl H2SO4 N
h� O
150°
C
Figure 2.33: Photochemical production of ε-caprolactam.
OH
O N H
(NH2OH)2 H2SO4 N O
H2SO 150°
C
4
Figure 2.34: Thermal production of ε-caprolactam.
costs associated with the generation of photons as well as with the chemical engineering aspects
can disqualify the photochemical route when compared to a thermal alternative. For photooxi-
mations the possibility to gain for example cyclohexanoneoxime through a direct route together
with the absence of any coupled byproduct renders this process attractive to produce the re-
quired intermediates for Nylon 6. The main advantage compared to the conventional process is
the absence of any stochiometric byproduct during the photoreaction (see Figure 2.33). Convert-
ing the produced oxime to the required ε-caprolactam by the Beckmann rearrangement directly
yields the intermediate of interest.[24,53] This reaction is conducted analogous to the thermal
process. Although the conventional pathway possesses a simple reaction path as well, the pro-
duction of large amounts of ammonium sulfate is a problem. Compared to the photochemical
process, (NH4 )2 SO4 is not only produced during the Beckmann rearrangement, but also during
the production of the cyclohexanoneoxime by use of hydroxylamine sulfate (see Figure 2.34).
With this, the total production of (NH4 )2 SO4 per amount of ε-caprolactam is lower for the pho-
tochemical route. An additional benefit is the high purity of the (NH4 )2 SO4 produced by the
photochemical process, which makes it possible to directly sell (NH4 )2 SO4 as fertilizer without
any further processing.[24]
2.2.7 Photohalogenation
2.2.7.1 General Aspects
Photohalogenations are in common cases addition or substitution reactions.[14,17,24,27,56] Pho-

tochlorinations and photobrominations are the most relevant members of this reaction type. The
reactions are radical chain reactions:
hν + Cl2 −−→ Cl• + Cl• (2.22)
36
2.2 Reaction Types
Figure 2.35: Photochlorinatoin of toluene at the side chain and aromatic ring.
hν + Br2 −−→ Br• + Br• (2.23)
The reactions start with the absorption of light, which provides enough energy for the disso-
ciation of the halogen-halogen bond. In pure solvents, the quantum yield can be considerably
higher than 10 000 for the photochlorination.
The thermal dissociation of the chlorine-chlorine bond requires temperatures greater than
200 ◦C and dissociation of bromine occurs between 250 ◦C to 400 ◦C. The minimum energy,
which is required to break the halogen-halogen bond for chlorine amounts to 240 kJ/mol and for
bromine 190 kJ/mol, which correspond to a radiation wavelength 500 nm and 630 nm.
2.2.7.2 Photochlorination
Photochlorinations give access to chlorinated products which are used as synthetic intermedi-
ates or solvents. Typical products are benzyl chloride, dichlormethane and tetrachlormethane.
Introduction of chlorine into polymers is also possible. This reaction type represents the most
commonly used photochemical reaction on industrial scale. The reaction proceeds through a
radical chain mechanism. Under suited reaction conditions, namely in the absence of impurities,
very large quantum yields can be reached. This is quite attractive for industrial application, be-
cause the required light intensity to achieve a certain production volume is lower. Equation 2.24
illustrates the general reaction step when chlorine is added to olefins.
hν
R−CH−CH−R + Cl2 GGGGGGA R−CHCl−CHCl−R + HCl (2.24)
Beside addition reactions, substitution can occur for photochlorinations. The most common
case is the substitution of a hydrogen atom, as generally shown in Figure 2.35. This reaction
path can be used beneficially for the chlorination of the side chains of alkylbenzenes. Although
addition to the aromatic ring remains possible, the reaction rates of the substitution are faster.
This enables selective introduction of chlorine into the side chain. Chlorination of the side
chain be further enhanced by use of moderately high reaction temperatures, because for such
37
2.2 Reaction Types
Figure 2.36: Product distribution of the photochlorination of toluene at 100 °C as a function of

the degree of chlorination.[24]
conditions, the addition to the aromatic ring becomes reversible. As a consequence, side chain
chlorination becomes the dominant reaction. Ring chlorinations become relevant, when the
ring is electrophilic. This can be provoked by addition of lewis acid catalysts such as FeCl3
or AlCl3 and is favored in polar solvents. Hence, metallic impurities must be removed from
the reaction solution to maintain high selectivities. This is especially important on an industrial
scale, because high purities of the solvents and reactants might not be possible due to technical
or economic reasons. In this case, complexing agents can be used to suppress ring chlorination
and the use of metals for construction should be avoided. Substitution on the aromatic ring is
favored for low reaction temperatures and high chlorine concentrations. The obtained product
distribution of the photchlorination of toluene is shown in Figure 2.36.[24]
Side chain chlorination of toluene and xylenes are of interest for chemical industries for the
production of intermediates for plasticiers, phtalic acid derivates and various other organic prod-
ucts with a world production of several tens of thousand tons. The chlorination at the side chain
becomes dominant when the temperature is moderately high and chlorine concentration low.
The reaction mechanism is similar to the radical substitution of saturated aliphatic hydrocar-
bons. The reaction steps can be controlled by variation of operating conditions. Depending on
the chlorination degree, the target product can be isolated.
2.2.7.3 Photobromination
The addition reactions of bromine to olefins are generally reversible and a radical chain mecha-
nism is accepted. To explain the stereoselectivity of the addition reaction, formation of a bridged
38
2.2 Reaction Types
bromoalkyl radical is proposed. The proposed mechanism is shown in Equations 2.25 and 2.26.
R Br
R Br
R'
R R' R R'
R' (2.25)
Br
Br2 Br R R'
R R' R R' R
R' Br (2.26)
The rotation around the C-C bond is prevented by formation of a bridged radical and for steric
reasons the trans-product is formed. The stereoselectivity can be explained by considering the
reaction rate of bromalkyl radical with bromine. Depending on the rotation rate around the
C-C bond and the reaction rate of the bromalky radical with bromine either the cis- or the trans-
product can be formed. The stereoselectivity of the product (cis or trans) depends on the stability
of the different rotational isomers of the radical as well as the steric hindrance of substituents.
Br R Br R R'
R' + Br
R R' R R' Br
Br Br (2.27)
Br R Br2
Br R' Br R' R
R + Br
R'
R R' R R' R R' Br
Br Br
(2.28)
2.2.8 Photosulfochlorination and Photosulfoxidation
Introducing sulfon groups into alkanes or alkyl aromates is of particular interest for the pro-
duction of anionic tensides. Alkane sulfonic acids/sulfonates show advantages when compared
to the often used alkylbenzoic sulfonic acids/sulfonates, because they possess better biological
degradation properties.[57] Despite this, it is problematic to produce these compounds on a tech-
nical scale. Alkane sulfonates with a backbone of 12 to 18 carbon-atoms are especially relevant
for chemical industries.
One possible synthesis route for alkane sulfonic acids utilizes photosulfochlorinations. These
reactions are initiated by breaking the Cl – Cl-bond through irradiation by light with a wavelength
of λ < 500 nm. The single reaction steps from initiation to propagation and termination are
summarized in Figure 2.37. When termination steps can be suppressed sufficiently, what can
be realized by use of reactants of high purity, quantum yields of φ > 4 · 104 can be reached.
39
2.2 Reaction Types
hν
SO2 −−→ SO2 ∗
RH + SO2 ∗ −−→ R• + HSO•2
R• + SO2 −−→ RSO•2
RSO•2 + O2 −−→ RSO2 O•2
hν
Cl2 −−→ Cl• + Cl• RSO2 O•2 + RH −−→ R• + RSO2 O2 H
RH + Cl• −−→ R• + HCl RSO2 O2 H −−→ RSO•3 + OH•
R• + SO2 −−→ RSO•2 RSO•3 + RH −−→ RSO3 H + R•
RSO•2 + Cl2 −−→ RSO2 Cl + Cl• OH• + RH −−→ H2 O + R•
hν hν
RH + SO2 + Cl2 −−→ RSO2 Cl + HCl RH + SO2 + 0,5 O2 −−→ RSO2 OOH
Figure 2.37: General reaction schemes of the photosulfochlorination and the photosulfoxida-
tion.
Due to impurities present in technical grade chemicals, the quantum yield is typically lower.
Photosulfochlorinations are associated with stoichiometrical formation of HCl.
Another way to generate sulfonic acid moieties are photosulfoxidations. These reactions are
initiated through exiting SO2 with a wavelength of 180 nm to 390 nm. The proposed mechanism
is shown in Figure 2.37. Excited SO2 transfers the energy to the alkane, resulting in abstraction
of a proton.[24] Compared to photosulfochlorinations, an important difference is the formation
of persulfonic acids (RSO2 O2 H) which decomposes into two radicals. Hence, the propagation is
maintained autocatalytically. Under ideal conditions, the reaction proceeds until full conversion
is reached with only a single, short irradiation. This reaction does not show any stoichiometric
byproducts. On an industrial scale, photosulfoxidations are conducted in the presence of water,
which acts as a radical scavenger. The light-water-process, implemented by Hoechst on a tech-
nical scale, uses water to suppress the formation and deposition of tarry substances at the reactor
wall. This avoids a decrease of the photon flux reaching the reaction solution. With this, the
performance of the process is maintained over time. Additionally, the alkane persulfonic acids
are decomposed to the corresponding alkane sulfonic acids and H2 SO4 .[58] In this case, the re-
action is not autocatalytic anymore and a permanent regeneration of radicals through irradiation
is required. The quantum yield in this case is φ ≈ 10. To increase the reaction rate, initiators can
be used.
40
2.2 Reaction Types
2.2.9 Photodesulfonation
The term photodesulfonation describes the elimination of a sulfonyloxy group ( – SO3 X – ) by

photochemical methods. Although there are few investigations on this reaction type, it offers an
application for some interesting experimental fields:
• the development of new synthesis routes,
• as protection for or blocking of functional groups,[59–61]
• the removal of sulfur-containing groups in waste water treatment,[62]
• the evaluation of photoreactivity and phototoxicity of sulfonamides used as drugs and
• the development of mechanistic models.
The thermal initiation of desulfonations usually needs harsh reaction conditions and only low
yields and selectivities can be accomplished.[63] By its directing effect, sulfonyloxy groups can
direct potential substituents to the desired position of e.g. an aromatic ring. The most stud-
ied substance families are substituted anthraquinone sulfonic acids (Aq – SO3 H), arenesulfonic
acids (Ar – SO2 OH) and their derived esters Ar – SO2 OR, amides Ar – SO2 NRR’ and aromatic
sulfones Ar – SO2 Ar.
The photochemical reactivity of these compounds is based on the sulfonyl group as the sul-
fur atom has no free electrons. For this reason, it has almost no conjugation effect with the
adjacent aromatic π-system, which significantly shifts the absorption spectrum of the aromatic
system allowing photonic excitation. The subsequently occurring excited states show reaction
characteristics similar to the non-sulfonated hydrocarbons. Thus, introducing the sulfonyloxy or
sulfonyl group to a hydrocarbon offers the possibility of subsequent photochemical conversion
at low temperatures as an alternative to the direct thermally conducted reaction of the hydrocar-
bons.
Arenesulfonic acids and their salts can be desulfonated by UV-light independent of the pH
value of the solvent. Keeping the reaction solution at room temperature, thermal desulfonation
can be avoided to allow an appropriate reaction control. The reaction can be of radical or ionic
character and may involve several excited states. In principle, three different reaction types can
be distinguished regarding desulfonation:
• desulfonation or substitution of a sulfonyloxy group by a hydrogen atom,
• substitution of a sulfonyloxy group by another functional group and
• dimerization under desulfonation.
41
2.2 Reaction Types
2.2.9.2 Desulfonation or Substitution of a Sulfonyloxy Group by a Hydrogen Atom
This reaction can be carried out in an aqueous solution in the absence of oxygen. A proton
adds to the excited molecule, forming a positively charged transition state. Finally, dehydra-
tion leads to the desulfonated aromate. Depending on the basicity of the aromatic ring caused
by the excitation, the yield varies from 2 % of the ortho-aminated compound to 50 % of the
para-aminated compound considering the example of anilinesulfonic acid.[64,65] The absorp-
tion spectra in strongly acidic solutions are similar to α-anthracene, α-anthraquinone and α-
anthrahydrochinone sulfonic acids. This suggests that the aromatic ring is not protonated in the
ground state but in the state of the lowest singlet excitation state S1 .[66]
hν
Ar−SO3 HGGGGGGAGGGAAr−H (2.29)
According to the relatively low yields, the quantum yields of desulfonation, that are in the range
of 3.5 · 10−4 to 1.4 · 10−2 , are rather small due to the high tendency of the protonated excited
state to simply deactivate again. Hereby, the order of the reactivity equals that of thermal ini-
tiation. The yield can be raised up to 90 % for e.g. anthraquinone sulfonic acid by working in
a basic alcohol solution, in the presence of amines and by using the whole absorption range of
the sulfonated molecule.[67] In the first step, an electron transferred from the alcoholate or the
amine yields a radical anion of the quinone system that is detectable via ESR spectroscopy.[68]
The increased lewis acceptor properties of the aromatic system in the exited state promotes the
electron transfer. If oxygen would be present, the additional electron would be transferred to the
oxygen with high yields disabling photodesulfonation to occur. The second step is the actual
photodesulfonation of at least one of the reduced forms under pH-dependent dismutation form-
ing either the monoanion A – SH – (pH above 10) or the dianion A – S2 – of the anthraquinone
system. Good yields are accessible for all substitution patterns as long as the photochemical
reduction to the anthrahydroquinone is possible. For example, nitro- or aminoanthraquinone
α-sulfonic acids do not react but form nonreactive charge-transfer states in the lowest excitation
state. Another possible hindrance of high yield desulfonation is the competing desulfonylation
forming SO2 in a photolysis process.
2.2.9.3 Substitution of a Sulfonyloxy Group by Another Functional Group
Alternatively to the substitution with a simple H-atom, some halogens or even whole functional
groups (e.g. NH2 or NO2 ) can substitute the sulfonyloxy group. Photosubstitution with halogens
can reach almost quantitative yields whereas several other substitutions are limited to about 45 %
42
2.2 Reaction Types
to 60 % because of secondary product formation by hydroxylation and amination of the aromatic

ring.[69]
hν
Ar−SO3 H + Br− GGGGGGAGGGAAr−Br (2.30)
The reaction rate can vary depending on the other substituents and their position on the aromatic
system, influencing the basicity of the molecule. The quantum yields and excitation wavelengths
are comparable to the ones of substitution by a hydrogen atom. The reaction mechanism for the
photosubstitution by e.g. a bromide ion starts with the transfer of an electron from the bromide
to an excited reactant molecule. Subsequently, the radical substitution of another molecule con-
taining a sulfonyloxy group promotes the formation of the brominated product. Besides SO2 ,
the hydroxyl radicals formed by decomposition of the dissociated HSO3 • radical are causal for
the secondary hydroxylation reactions.
2.2.9.4 Dimerization Under Desulfonation
hν
Ar−SO3 HGGGGGGAGGGAArH + Ar−Ar (2.31)
Photodesulfonation of benzenesulfonic acids and most of their salts leads to either the corre-
sponding hydrocarbons Ar – H or the dimerization product Ar – Ar. The yield mainly dependents
on the reaction conditions and usually varies from 5 % to 34 %. The initial key step is the ho-
molytic scission of the Ar – S-bond after irradiative excitation. Dimerization with another non-
excited starting molecule as well as recombination gives the biarylic compound. Alternatively,
the corresponding hydrocarbon is the product of an aryl radical with a suitable hydrogen donor,
e.g. a simple hydrocarbon. As already mentioned in section 2.2.9.3, the HSO3 • radicals de-
compose preferably in acidic solution into SO2 and OH – to form in sum quantitative amounts of
sulfur dioxide, sulfuric acid and hydrogen peroxide. In some cases, a hydroxylated arylic species
can start a polymerization ending with polyphenolic products.[70] In addition, a potentially in-
teresting option in synthesis is the photolysis of α-substituted cyclic sulfones to hydrocarbonic
ring systems (cyclopentenes and cyclobutenes) by reducing the ring size from six to five or even
from five to four carbon atoms. This path is also possible for the transformation of episulfones
into alkenes, 3-sulfolenes into 1,3-dienes or diketosulfones into diones (Figure 2.38). All these
reactions can only be carried out photochemically because if thermally initiated, the reactants
would decompose to a significant amount.
43
2.2 Reaction Types
R R R R
h� C C
H H diethylether H H
s
o2 SO h�
2
benzene
O
O O
h�
so2 so2 +
methanol
O O
O
Figure 2.38: Transformation of an episulfone into an alkene, a 3-sulfolene into an 1,3-dienes

and a diketosulfone into a dione.[24]
2.2.10 Photodecarbonylation
Removing a carbonyl group by irradiation with UV light is called photochemical decarbony-

lation or photodecarbonylation. The reaction takes place by photoelimination of a small but
stable CO molecule. The steps of reaction can be described as C – C-bond-breaking and C – C
bond-formation, so it is considered a concerted reaction that follows trajectories determined by
orbital symmetry. Photoinduced eliminations of carbonyl groups are endothermic reactions. The
energy for the reaction results from the absorption of a photon. Due to this, the products have a
higher energy content than the starting material.[27] For this kind of reaction high pressure xenon-
mercury lamps with emission in the UV region are usually used. The reaction takes place under
irradiation with wavelengths of 200 nm to 400 nm. Several saturated cyclic and aromatic ketones
as well transition metal carbonyl complexes undergo photochemical decarbonylations.[71]
The photodecarbonylation of thujone is shown in Figure 2.39.[71] Under given conditions the
CO formation rate is 0.79 mL min−1 , yielding a diene as product. The irradiation of tetramethyl-
1,3-cyclobutanedione in benzene gives mainly 2,3-dimethyl-2-butene (tetra-methylethylen). As
shown in Figure 2.40, it is assumed that the reaction proceeds via an intermediate and the for-
mations of tetramethylcyclopropanone. The product is obtained in small yield when methanol is
used as solvent. Major products are methyl isobutyrate and methyl 2,2,3-trimethylbutyrate. The
44
2.2 Reaction Types
Figure 2.39: Photodecarbonylation of thujone.[71]
O
O O
hv
- CO - CO
O
Figure 2.40: Photodecarbonylation of tetramethyl-1,3-cyclobutanedione.[72]
Figure 2.41: Photodecarbonylation of dispiro[5.1.5.1]tetradecane-7,14-dione.[72]
O
hv
- CO
Figure 2.42: Photodecarbonylation of diphenylcyclopropenone.[73]
irradiation of dispiro[5.1.5.1]tetradecane-7,14-dione in benzene and methylene chloride under

avoidance of oxygen gives bicyclohexylidene associated with the release of carbon monoxide
(see Figure 2.41).[72] The photodecarbonylation reactions of aromatic ketones proceed rapidly
and almost quantitatively. Irradiation of diphenylcyclopropenone gives diphenylacetylene as
product and furnishes a yield of 68 % (see Figure 2.42).[73]
2.2.11 Photochemical Reactions of Metal Complexes
The absorption of light by a metal complex causes a change of the coordination sphere. Conse-
quently, this physical process can lead to photochemical reactions as well. The d-ortbitals of the
central metal can lead to more than two states of spin multiplicity. Hence, the number of excited
states is larger for metal complexes than for colored organic compounds. This also results in dif-
45
2.2 Reaction Types
ferent reactions that can be initiated by absorption of light. Among the possible reaction types
are photodissociation, photosubstitution, geometrical photoisomerization and photooxidation-
reduction reactions.[74,75]
2.2.11.2 Photosubsitution Reactions
Absorption of light that induces π → π ∗ -transitions of the ligand or d-d-transitions of the metal
causes changes of the electron density distribution of the whole complex. With this, the metal-
ligand bond can be weakened and dissociation of this bond can occur. This process is called
photodissociation. The product of this reaction is a metal complex with an unoccupied coordi-
nation position, which is typically unstable.[74,75] An example is the dissociation of CO from a
Cr3+ complex:
hν
[Cr(CO)6 ]3+ −−→ [Cr(CO)5 ]3+ + CO (2.32)
The free position can be occupied by another molecule. Typical examples for such photosubsti-
tution reactions are the substitution of a ligand with another one. In coordinating solvents the
substituting ligand can be a solvent molecule. This reaction type is called photosolvatation. For
an ammonia complex of chrome [Cr(NH3 )6 ]3+ , one of the ammonia ligands can be exchanged
by a water molecule.[74]
hν
[Cr(NH3 )6 ]3+ + H2 O −−→ [Cr(NH3 )5 (H2 O)]3+ + NH3 (2.33)
Photoaquation Reactions The most common photochemical reaction in aqueous solutions

is the substitution of a ligand with water. An example of these so called photoaquation reactions
is the light-induced exchange of water with another water ligand. The exchange of water can
be followed by isotope labeled H2 O18 . The quantum yields (φ ) of these reactions are very low
(Φ≈ 0.02) and independent from the wavelength. These low quantum yields can be explained
with a mechanism involving labilization of a water ligand in the excited state.[76]
hν
[Cr(H2 O)6 ]3+ + 6H2 O18 −−→ [Cr(H2 O18 )6 ]3+ + 6H2 O (2.34)
The photoaquation reaction of the chromium chelate complex with ethylenediamine (en)
Cr(en)3 3+ leads to substitution of the coordinated ethylenediamine by an acid (H3 O+ ), followed
by protonation of the nitrogen on the free "hinged" ethylenediamine of the chelate. A consecu-
tive second photoaquation follows with exchange of the protonated ethylenediamine by another
water molecule. The formation of Cr(en)2 (enH)(H2 O)4+ can be followed by using a pulsed
laser. The complex is formed within 20 ns and a reaction rate constant (k≥108 s−1 ) for a pseudo
46
2.2 Reaction Types
first-order reaction was found.[77] Quantum yields of some photoaquation reactions of chromium
complexes with different ligands are shown in Table 2.3.
hν
[Cr(en)3 ]3+ + H3 O+ −−→ [Cr(en)2 (enH)(H2 O)]4+ (2.35)
hν
[Cr(en)2 (enH)(H2 O)]4+ −−→ [Cr(en)2 (H2 O)2 ]3+ + enH (2.36)
Table 2.3: Photoaquation quantum yields.

Complex Φ Complex Φ NH3 Φ X– Lit.
Cr(H2 O)6 3+ 0.02 CrCl(NH3 )5 2+ 0.36 0.005 [76]
Cr(NH3 )6 3+ 0.3 CrBr(NH3 )5 2+ 0.34 0.009 [78],[79]
Cr(en)3 3+ 0.37 Cr(NCS)(NH3 )5 2+ 0.4 0.02 [77]
Cr(CN)6 3− 0.12 [80]
Cr(NCS)6 3− 0.26 [78]
Cr(urea)6 3+ 0.1 [78]
Cr(oxalate)6 3− 0.09 [81]
Geometrical Photoisomerizations Substitution of ligands in complexes with different lig-

ands can cause a change of the stereochemistry of the complex. For example, a square-planar
cis-complex can isomerize to a trans-complex:
cis−[Pt(py)2 ]Cl2 −−→ trans−[Pt(py)2 ]Cl2 . (2.37)
One ligand dissociates from the complex first and subsequently recoordinates again on a different
position. During the time after the complex lost one ligand, the remaining ligands can change
position, so that a different isomer results.
2.2.11.3 Photooxidation-Reduction Reactions
When metal complexes are irradiated with light that matches the MLCT or LMCT bands of the
complex, the absorption of radiation can lead to intramolecular electron-transfer reactions. The
photoredox behavior is induced by the change of redox-potentials during absorption of light.
The changing oxidation state of the metal can cause decomposition of the whole complex, as
shown below:
2 [FeIII (C2 O4 )3 ]3− −−→ 2 FeII + 5 C2 O4 2− + 2 CO2 (2.38)
47
2.2 Reaction Types
This reaction can be used as chemical actinometer to measure the photonflux (see section 2.3.4.2).
2.2.12 Photoinduced Radical Polymerization
Radical polymerization is the best-evaluated method to form a polymer by successively adding

monomers that have formed radicals. Due to the availability of numerous monomers and the
simple process control, radical polymerization is one of the key techniques in large scale in-
dustry. According to all chain-growing reactions, the polymerization splits into the main steps
of initiation, chain growth, chain termination and dimerization. Several initiator molecules can
be used to start the process of growing a polymer chain. The activation energy varies from
45 kJ mol−1 for thermal to 25 kJ mol−1 for photochemical initiation.[82] Radical formation has to
be initiated in situ to avoid immediate deactivation, so reaction control by irradiation offers great
advantages for safety and regulation issues. Homolytic dissociation of a photo labile single bond
in the initiator gives two starting radicals:
hν
IGGGGGGA2 R• (2.39)
Several peroxides or hydroperoxides, azo compounds and arylketones can undergo this reac-
tion. More specific, popular examples for these photochemically cleavable substance classes are
dibenzoyl peroxide (BPO), tert-butyl hydroperoxide, azobisisobutyronitrile (AIBN) and benzoin
(see Figure 2.43). Although the photochemical pathway do not depend on temperature directly,
some heating to 40 ◦C to 70 ◦C is required to keep the subsequently ongoing polymerization
reaction running.[82] Two examples of initiation reactions are shown below:
hν
Ar−CO−CO−Ar + RHGGGGGGAAr−CO−ĊOH−Ar + R• (2.40)
hν
Mn2 (CO)10 + CCl4 GGGGGGA0.5 Mn2 (CO)10 + •CCl3 (2.41)
Photochemical initiation is followed by the advancing chain building process and termination.
These processes do not differ from the processes initiated by thermal activation.
2.2.13 Cationic Photopolymerization
Photoinitiated cationic polymerizations are widely used in different applications like photocur-
able coatings, inks, and adhesives.[83] This type of reactions is usually initiated by photoini-
tiators that are based on iodonium and sulfonium salts that absorb at λ < 300 nm and in the
range of 380 nm to 400 nm.[84] Contrary to the free-radical photopolymerization, which experi-
48
2.2 Reaction Types
CH3 O
OH O
O O
H 3C
H 3C
O
tert-butyl hydroperoxide dibenzoyl peroxide
N O
H 3C
C CH3
N
N
H 3C C
CH3
N
O
azobisisobutyronitrile benzoin
Figure 2.43: Some photochemically activatable radical initiators.
ences rapid termination of the polymerization process when the light source is removed (due to
radical-radical termination reactions), the cationic polymerization processes proceed long after
the irradiation has been ceased. Typically, the reaction stops when almost all monomer has been
consumed.
Due to a better solubility in non-polar monomers, diaryliodonium salts are usually preferred
instead of the corresponding triarylsulfonium salts. For the cationic polymerization the four
most commonly used cations are in the order of popularity:[83]
MtXn − = BF− − − −
4 < PF6 < AsF6 < SbF6 .
The mechanism of the UV-induced photolysis of diaryliodonium salts (Ar2 I+ MtXn − ) is very
complex, but it is possible to show it in an abbreviated form:
( )
Ar2 I• + MtXn − + Ar•
hν + Ar2 I+ MtXn − −−→ 1[Ar2 I+ MtXn + ] −−→ −−→ HMtXn (2.42)
ArI + Ar+ MtXn −
Photoexcitation of the diaryliodoniumsalt is the first step, followed by both heterolytic and ho-
molytic cleavages of the carboniodine bond of the resulting excited singlet state. This leads to
simultaneously formed free-radical, cationic and cation-radical fragments. The aryl cations and
aryliodine radicals generated during this process are highly reactive and react with monomers
49
2.2 Reaction Types
Figure 2.44: Common monomers for cationic polymerization.[83]
or impurities to give the protonic acids, the so called “super acid” HMtXn . This “super acid” is
able to react with the monomer (M) and induce the cationic polymerization:[85]
HMtXn + M −−→ H−M+ + MtXn − (2.43)
The subsequent propagation steps are identical to common cationic polymerizations.
M+ + M −−→ M−M+ (2.44)

nM
M−M+ −−→ [M−]n M+ (2.45)
Typically, there is no chain termination reaction, the reaction stops with the total consumption
of the monomer. Common monomers (M) for this reaction are shown in Figure 2.44.
2.2.14 Photoinduced Polyaddition for the Synthesis of PUR
Polyurethane polymers (PUR) are build up from organic units linked by urethane units. Fig-
ure 2.45 shows the basic mechanism of the formations of a link in PUR by polyaddition and the
resulting urethane group. Chain propagation can be achieved by using polyisocyanates and poly-
ols as monomers. Since a wide range of different monomer units with functional groups and a
varying number of end groups can be used for the production of PUR, the range of polyurethane
50
2.2 Reaction Types
Figure 2.45: Mechanism for the formation of an urethane unit by polyaddition.
Figure 2.46: Proposed mechanisms for the reaction of phenyl isocyanate with 2,2,2-
trifluoroethanol or ethanol.[87]
polymers and plastics is similar broad. The production of PUR was reported first by O. Bayer in
1937.[86]
The polyaddition reaction begins with a nucleophilic attack of the alcohol to the carbon atom
of the isocyanate. Electron density is shifted towards the isocyanates’ nitrogen atom and a
secondary amine is formed with the alcohols’ hydrogen. This reaction is often catalyzed by
deprotonation of the alcohol, e.g. by tertiary amines.
A photochemical induced polyaddition of urethanes was reported by M ARQUET ET AL . in
2014.[87] The reaction of polyfluorinated alcohols and phenyl isocyanate yields new highly fluo-
rinated urethanes. The proposed reaction mechanism is given in Figure 2.46. It was also shown,
that the reaction with not fluorinated alcohols is not induced by UV-light. In contrast to the
mechanism with not fluorinated alcohols, the fluorinated alcohol is much less nucleophilic and
more acidic. Hence, the formations of a strong hydrogen-bonding complex between the alcohol
and isocyanate is proposed. Radiation then initiates proton shift and nucleophilic addition.
Another way to use UV-light for the formation of polyurethanes is the use of photoinitiators.
In contrast to the mechanism shown above, polymerizations initiated with photoinitiators in most
cases are free radical polymerizations. For polyurethanes, UV-light is often used for curing or
crosslinking of polyurethane coatings. This provides an easy application of the coating, which
51
2.2 Reaction Types
Figure 2.47: Synthesis of H10 and UV-curable waterborne hyperbranched polyurethane disper-
sion (WHPUD).[88]
then can be cured with a controllable process. Highly crosslinked polymers can be produced as
shown in Figure 2.47. The hyperbranched polyester H10 is used as core molecule. By joining
polyurethane chains to the core molecule and subsequent dispersing this hyperbranched polymer
with photoinitiator in water, a UV-curable waterborne hyperbranched polyurethane dispersion
can be produced. This dispersion can for example be deposited as a film and cured with UV-
light. Within this process the number of double-bond-groups (C – C) is increased.[88]
2.2.15 Photoinduced Ring Opening Metathesis of Cyclic Olefines
Ring opening metathesis is a catalyzed metathesis reaction of cyclic olefines and used in most
cases for chain growth polymerization. Often used catalysts are Grubbs ans Shrock type metal
complexes. A commonly used monomer is norbonene, which is shown in a simplified catalytic
52
2.2 Reaction Types
Figure 2.48: Simplified ring opening metathesis polymerization cycle with norbonene.
Figure 2.49: Model for the formation of the active ROMP catalyst species from a sandwich
precatalyst.[93]
cycle in Figure 2.48. The metal catalyst is opening and joining cyclic olefines. Until now,
a wide variety of catalysts and monomers is known, opening the possibility to produce tailor
made polymers.[89]
With the use of “switchable” catalysts for ring opening metathesis polymerization (ROMP),
the polymerization can be triggered exactly at the desired moment. This is desirable for many
technical applications. A common technique is to prepare a monomer-precatalyst mixture, that
is storable over a period even at elevated temperatures (usually < 45 ◦C). Most used precatalysts
can be activated thermally. However, there are also UV-triggerable precatalysts.[90,91] These sys-
tems are of interest for example for photolithography in microfabrication.[92] A UV-triggerable
ruthenium sandwich catalyst system was presented by K ARLEN et al. in 1995.[93] The model
for the formation of the active species is shown in Figure 2.49. The precatalyst is a ruthenium
sandwich complex, that decomposes into a complex with solvent molecules as ligands when
irradiated with UV/VIS radiation (330 nm to 500 nm, Hg-lamp). The polymerization rate is de-
termined by the degree of decomposition of the precatalyst. Hence, the overall reaction rate can
be controlled by the light intensity or the period of irradiation.
A more advanced system was developed by L EMCOFF et al. (see Figure 2.51a). The sulfur-
chelated ruthenium precatalysts can be isomerized by UV-light with a wavelength of 350 nm
from a cis-dichloro to a catalytic active trans-dichloro isomer. As a reason for the isomerization,
53
2.2 Reaction Types
Figure 2.50: General reaction schemes of cross metathesis, ring-closing metathesis and ring-
opening metathesis.[94]
(a) (b)
Figure 2.51: (a) Proposed photoisomerization of a sulfur chelated ruthenium complex.[95] (b)
Activation of a sulfur-chelated ruthenium catalyst with supersilyl NHC endgroups
with 350 nm light.[96]
the modification of the sulfur chelatation is proposed. This type of catalyst can be used for dif-
ferent metathesis reactions such as cross, ring-closing and ring-opening metathesis.[94,95] These
types of metathesis are shown in Figure 2.50. By functionalizing the N-heterocyclic carbene
(NHC) with supersilyl endgroups, not only the activation, but also the decomposition of the cat-
alyst and thus the end of the reaction can be triggered. The catalyst shown in Figure 2.51b can be
transferred to the catalytic active trans state with UV-light with a wavelength of 350 nm. In ad-
dition, the catalyst deactivates when irradiated with UV-light with a wavelength of 254 nm.[96]
A reactivation of the catalyst by UV-light was not yet reported, however, the development of
systems that can be triggered with different wavelengths for different reactions is desirable.[97]
2.2.16 Photohydrodimerization
Some carbonylated compounds (ketones, aldehydes) can be excited by irradiation due to a chro-
mophore and subsequently be reduced by adding a hydrogen atom from an appropriate hydrogen
donor (an alcohol, hydrocarbon or amine). In a second step, two intermediate ketyl radicals can
combine and form a 1,2-ethanediol. This photoinduced two-step-process including reduction
54
2.2 Reaction Types
Figure 2.52: Reaction scheme of the photohydrodimerization with activation, hydrogen abstrac-
tion and dimerization.
and dimerization is called photohydrodimerization. The general reaction scheme is given in

Figure 2.52.
The products of the photohydrodimerization belong to the substance class of pinacols and
are of remarkable interest on an industrial scale as precursors for pharmaceuticals or fertiliz-
ing agents. After the discovery of C HIAMICIAN and S ILBER,[98] who reached good yields for
the photohydrodimerization of benzophenone to benzopinacol, only some additional research
effort was needed to bring pinacolizations to large scale industry.[72,99–102] The product of main
interest was 3,4-diphenyl-1,2,5,6-tetrahydrobenzoic acid whose derivatives allow the active reg-
ulation of plant growth. The initial step in the synthesis route is the photohydrodimerization of
acetophenone.
The kinetics of the reaction are primarily effected by the hydrogen abstraction rate constant
(second row in Figure 2.52), that changes with the nature and energy level of the excited ketone,
the homolytic dissociation energy of the H – B-bond of the hydrogen donor, steric and polar
effects, the solvent, excited state quenching factors and their interactions. In either case, if the
lowest energy excited state occurs as singlet or triplet state of the (n, π ∗ ) electronic configuration
at the carbonyl group, the ketone is most reactive. In triplet state, the reactivity is even compa-
rable to alkoxy radicals, explaining the high driving force to dimerization. This differs from the
singlet state where basically a fast intersystem crossing (compare section 2.1.5.2) limits a faster
reaction rate.
Considering amines as hydrogen donors, their ionization potential plays an important role. A
lower ionization potential leads to a higher reactivity, thus tertiary amines are the most reactive
ones. Hereby, the reaction mechanism may change from hydrogen transfer corresponding to
55
2.2 Reaction Types
a high ionization potential to an electron transfer mechanism when the ionization potential is
rather low. If both the ionization energy and the bond dissociation energy of the hydrogen
donor are high, hydrogen abstraction will not occur in substantial amounts (e.g. acetonitrile
in water). Alternatively, other photochemical reactions like the N ORRISH type I reaction (see
section 2.2.3.1) can become more favorable, especially at temperatures above room temperature.
Another possible reaction pathway is the reduction of the carbonyl group to the corresponding
alcohol, that occurs when the ketone is sterically hindered. After abstraction of the first hydrogen
atom, a second hydrogen atom is abstracted or immediate disproportion to the alcohol happens.
Regarding the total quantum yield Φp of photohydrodimerizations following the scheme from
Figure 2.52, three key step quantum yields can be defined:
• the intersystem crossing efficiency ϕISC , i.e. the quantum yield for the formation of the
triplet state,
• the radical formation efficiency from the excited state of the ketone, thus the hydrogen
transfer efficiency ϕh influencing the rate constant of hydrogen absorption kh and
• the dimerization efficiency forming pinacols out of the ketyl radicals ϕr .
This results in a total quantum yield of
Φp = ϕISC ϕh ϕr , (2.46)
kh [HB]
ϕh = . (2.47)
kh[HB] + ∑ kd
kd sums up all parallel occurring deactivating rate constants of first or pseudo-first order for
the triplet state of the ketone. It is important to note that these equations are only valid for
reactions proceeding in the absence of oxygen as it quenches the triplet state, forcing ϕh to
become almost negligible. Hence, the reaction is typically carried out under inert gas conditions
and the concentration of the hydrogen donor is raised by using it as undiluted solvent if possible.
That way, ϕh approaches unity letting the efficiency of hydrogen absorption reach almost 100 %.
2.2.17 Photocatalytic Water Splitting
Energy generation from fossil fuels is a major environmental problem since it is associated
with the emission of gases such as nitrogen oxides, sulfur oxides and carbon dioxide. One
possibility to reduce the share of fossil fuels is the use of hydrogen as energy source generated
from renewable resources.[103] Beside electrolysis of water by using renewable energy sources,
water can be splitted into hydrogen and oxygen via photocatalytic processes.
Photocatalytic water splitting has been investigated extensively since its first discovery.[104–106]
F UJISHIMA and H ONDA used an n-type titanium dioxide as photoanode and a platinum counter
56
2.2 Reaction Types
electrode. The authors have shown that oxygen evolution occurs at the photoanode and hydro-
gen evolution at the cathode, when titanium dioxide is irradiated and an external or chemical
bias is applied.[105–107] See Figure 2.53 for a schematic illustration of the relevant processes.
The first step of photocatalytic water splitting is charge separation, which is caused by irradia-
tion of a photocatalytic active semiconductor, such as TiO2 , with an energy greater than the band
gap of the semiconductor. Electrons and holes are generated at the photoanode (Equation 2.48).
2 h ν −−→ 2e- + 2 h+ (2.48)
The generated holes can subsequently oxidize water, so that O2 and H+ ions are generated (Equa-
tion 2.49). Afterwards H+ ions are transported through an electrolyte to the cathode.
1
2 h+ + H2 O −−→ O2 + 2 H + (2.49)
2
The transport of electrons from the anode to the cathode via an external circuit can lead to the
reduction of H+ ions at the cathode.
2 H+ + 2 e− −−→ H2 (2.50)
The complete reaction equation of photocatalytic water splitting can be written as
1
2 hν + H2 O −−→ O2 + H2 . (2.51)
2
The overall photocatalytic reaction takes place only when the absorbed photons have equal or
more energy than the band gap of the photoanode. The rutile modification of TiO2 exhibits a
band gap of 3.0 eV and therefore can absorb light with a wavelength of less than 420 nm.[106] As
a consequence, only UV light can be utilized to drive photocatalytic water splitting. When the
use of solar light is considered, this situation is problematic since only 4 % of the total photon
flux is emitted in the UV region.[108] Figure 2.54 illustrates the solar spectrum recieved at earth’s
crust. It is evident, that the discussion of the fraction of light, which can be used for generating
hydrogen, becomes even more relevant when the photon fluence rate is considered instead of the
irradiance.
Thermodynamically 1.23 eV are required to split water into hydrogen and oxygen. Because
of the energy losses that occur in practice, the potential to apply to a photoelectrochemical cell
(PEC) is typically above 2 V. A photoanode, which exhibits a band gap of 2 eV can absorb light
up to 620 nm. This would enable the absorption of roughly 30 % of the total solar irradiation
and gives the maximum energy conversion efficiency that can be achieved in practice. B OLTON
57
2.2 Reaction Types
Figure 2.53: General function principle of photocatalytic water splitting.[107]

IR VIS UV
54 % 42 % 4%
λ /nm
4000 1240 827 620 496 413 354 310 280
-06
8·10 1.6
800 nm 400 nm
7·10-06 1.4
ṅPhoton /(mol/s/m2 /nm)
-06
6·10 1.2
Ee /(W/m2 /nm)
5·10-06 1
-06
4·10 0.8
-06
3·10 0.6
2·10-06 0.4
-06
1·10 0.2
0 0
0.31 0.5 1 1.5 2 2.5 3 3.5 4 4.43
E/eV
terrestrial photon irradiance ṅPhoton terrestrial irradiance Ee
Figure 2.54: Solar irradiance Ee and photon fluence rate ṅPhoton recieved on earth’s crust (AM
1.5 solar spectrum).[108]
et. al. discussed in detail the efficiencies of photocatalytic water splitting.[109] The authors
assumed a value for unused energy per photon (Uloss ) of about 0.8 eV and a realistic maximum
efficiency of 17 % for a practical system.[109] Major problems of photocatalytic water splitting
with conventional photo catalysts are, on the one hand the large band gap of the catalysts and on
the other hand the positions of valence band (VB) and conduction band (CB).[110] In Figure 2.55
the band gap energies of some oxide materials are shown. It becomes clear, that the mentioned
problems of a large band gap and the required position of the bands are similar for a great
number of photocatalysts. This explains the current large research efforts on new photocatalysts
with narrower band gap.[107,111]
The most commonly used and studied semiconductor photoanodes consist of the following
58
2.2 Reaction Types
Figure 2.55: Band gap energies of different metal oxide materials.[110–112]
materials: TiO2 , SrTiO3 , WO3 ZnO, Fe2 O3 , BaTiO3 and CeO2 .[110–116] The oxidation of water
on TiO2 photoanode yields oxygen. The reduction takes place at e.g. a platinum cathode, where
hydrogen is produced. To increase the efficiency of a PEC, factors such as voltage, anode and
cathode materials and light intensity can be varied.[117]
Another possibility for light driven water splitting is the use of two different photocatalytic
active materials. The irradiation of photocatalytic active materials enables the generation of
holes at the photoanode and electrons at the photocathode. This type of PEC requires a redox
couple (I – /IO3 – ) as electron mediator.[118] In this system, a photoanode (WO3 ,TiO2 ) for the
oxygen evolution reaction (OER) and a photocathode (SrTiO3 : Cr/Ta) for hydrogen evolution
reaction (HER), are used. In the first step, water is reduced to hydrogen by a photoelectron
at the photocathode and the mediator is oxidized. In the second step, the oxidized mediator
is transported through the electrolyte to the photoanode and is reduced to oxygen by the pho-
toinduced holes. Photocatalytic water splitting by two step photoexcitation with two different
semiconductor photocatalysts has been known as so called “Z-System”.[119–121]
A different approach for utilizing a larger fraction of the solar light is the use of tandem cells,
consisting of more than one material absorbing the light.[122–124] Typically, this is realized by
stacking different materials on each other so that the first layer absorbs only a fraction of the light
and the remaining fraction is absorbed by the underlying layer. However, the manufacturing of
such electrodes is complex and often the long term stability is not given.
59
2.2 Reaction Types
2.2.18 Phototransduction
Phototransduction describes the process of converting light to electrical signals in a photore-

ceptor cell in the eyes of vertebrates. These species rely on retinal rods and cones to form
image-like vision. Rods are remarkably sensitive, being able to transduce the absorption of
a single photon. Cones are responsible for vision at daylight conditions. The higher tempo-
ral resolution of the cones causes a loss of sensitivity towards light. Depending on the num-
ber of different types of opsines present in the eye, color vision is more or less distinctive.
Each photopsine, always bound to the same chromophore retinal, gives an additional color im-
pulse. Humans have rhodopsin (λmax = 500 nm) for brightness vision in the rods and cyanopsin
(blue, λmax = 420 nm), iodopsin (green, λmax = 522 nm) and porphyropsin (red, λmax = 543 nm)
in the cones for color vision. The mouse has become a popular animal model for studies
of the phototransduction in vertebrates over the last decades due to the similarity to primate
photoreceptors.[125,126] Neglecting the cell body itself, rods and cones basically consist of three
functional regions (Figure 2.56):
1. the outer segment is made of membrane disks with spaces of about 28 nm. Besides other
transduction components, the disks contain the visual pigments rhodopsin in rods and
cone pigments in cones. In rods, the disks are internalized and thus separated from the
plasma membrane. The disks of the cones are placed directly on the plasma membrane,
offering a larger surface area for e.g. rapid chromophore transfer to regenerate pigments.
Both are renewed progressively to maintain a constant outer segment length and with this
the sensitivity towards light.
2. the inner segment consists of the endoplasmatic reticulum and the Golgi apparatus. A high
density of mitochondria allows to meet the high energy demands of the phototransduction
process.
3. the synaptic terminal transmits the incoming light signal to the second-order neurons in
the retina.
The rhodopsin molecule in the rods turns enzymatically active upon absorbing a photon. This
happens by transforming the light-sensitive molecule 11-cis-retinal to all-trans-retinal, leading to
the separation of the retinal from the protein component of the rhodopsin. Subsequently, a signal
transfer and enzyme activation cascade resulting in a closed ion channel for Na+ and Ca2+ in the
plasma membrane follows.[128] In the absence of light, the open channels for both Na+ /Ca2+ and
K+ ions provide an inward current to depolarize the membrane. Accordingly, closing only the
Na+ /Ca2+ channel causes a hyperpolarization at the membrane and a decrease in the release of
exciatory neurotransmitter as the K+ channels are still open. Until the opsin is deactivated by
phosphorylation and chemically bound to arrestin, the closed channel forces a neuronal signal
60
2.2 Reaction Types
Figure 2.56: Structural drawing of the photoreceptors and the channel system. The three re-
gions of photoreceptors are shown on the left: the outer segment, the inner seg-
ment and the synaptic terminals. The sodium ion channels gated by messenger
nucleotides are depicted on the right: In the dark, the channels are open causing a
depolarized membrane. Closing the channels under the influence of light generates
a distinct membrane potential.[127]
of about 40 mV to be sent to the retina for about 0.4 s.[129]

After a complicated reactivation process by the retinal isomerase, all-trans-retinal is returned
to 11-cis-retinal (see Figure 2.57) and can be reinserted into opsin.[130] The absorption maximum
of 11-cis-retinal lies at about 498 nm in the range of green light.
61
2.2 Reaction Types
Figure 2.57: The chromophore 11-cis-retinal can be transferred to all-trans-retinal by the ab-
sorption of light.
2.2.19 Photosynthesis
Photosynthesis is a process performed by organisms to convert light energy into chemical en-
ergy. Around 40 % of the plants dry mass as carbon is produced by photosynthesis.[131] The
photosynthetic process is usually divided in two types: oxygenic photosynthesis and anoxygenic
photosynthesis.[132] The anoxygenic photosynthesis is typically performed by bacteria without
releasing oxygen but e.g. sulfur. Due to the complexity of the topic, this section will only give a
short overview over the oxygenic photosynthesis.
Oxygenic photosynthesis is most common and performed by plants, algae and cyanobacteria.
In the oxygenic photosynthesis, usually electrons are transferred by light energy from H2 O to
CO2 . Thus, CO2 is reduced and H2 O is oxidized by finally releasing O2 and producing carbo-
hydrates.
Mechanism It is possible to divide the (oxygenic) photosynthesis into three main processes:
• absorption of photons by pigments,
• transport of electrons from water splitting, production of nicotinamide adenine dinu-
cleotide phosphate (NADPH) and adenosine triphosphate (ATP) (“light reactions”) and
• the carbon-reduction cycle under consumption of ATP and NADPH (“dark reactions”).
The absorption of photons by pigments, mainly by chlorophylls, is associated to two reaction
centers, photosystem I (PS I) and photosystem II (PS II). The pigments are embedded in mem-
brane structures and absorb a major part of the photosynthetically active radiation (400 nm to
700 nm).[131] This leads to an excitation of an electron.
Light Reactions PS I is a chlorophyll dimer with an absorption maximum at 700 nm. The
reaction center of PS II contains redox components including chlorophyll α with an absorption
maximum of 680 nm. For the formation of one oxygen molecule out of two water molecules, 8
photons are needed – 4 photons have to be received by PS I and 4 photons by PS II.[15] PS II is
responsible for water splitting. With 4 photons, a 4-electron-oxidation of plastoquinone (PQ) to
62
2.2 Reaction Types
Figure 2.58: Simplified scheme of the interactions of the different reaction centers. The reac-
tions at the different sites are given in equations 2.52 - 2.57.
plastohydroquinone (PQH2 ) is initiated, that leads to the formation of water and the production
of elementary oxygen:
PS II : hν + 2 H2 O + 2 PQ −−→ O2 + 2 PQH2 (2.52)
The cytochrome b6 f complex (Cytb6 f ) transports the resulting electrons to the reaction center
of PS I. PQH2 and plastocyanin (PC) work as mobile electron transport molecules.
Cytb6 f : PQH2 + 2 PCox −−→ PQ + 2 PCred + 2 H+ (2.53)
The PS I reaction system is responsible for the regeneration of NADPH in a 2-electron reduction
step:
PS I : hν + H+ + 2 PCred + NADP+ −−→ 2 PCox + NADPH (2.54)
At the same time, protons are transported to the cell membrane with embedded thylacoides,
where ATP is regenerated:
+
ADP3− + HPO2−
4 + H −−→ ATP
4−
+ H2 O (2.55)
63
2.2 Reaction Types
Dark Reactions The enzymatic reduction of CO2 in the so called Calvin-cyclus does not need
further photons. The reaction can be described by the following equation:
2 NADPH + 3 ATP4− + 3 H2 O + CO2 −−→

2 NADP+ + ADP3− + 3 HPO2− +
4 + H + [CH2 O] + H2 O (2.56)
In sum, the dark and the light reactions can be expressed simplified as follows:
hν + 6 CO2 + 12 H2 O −−→ C6 H12 O6 + 6 O2 + 6 H2 O (2.57)
Figure 2.58 illustrates the interaction between the different reaction steps in a simplified scheme.
64
2.3 Technical Aspects
2.3.1 Light Sources
The choice of the light source is probably the most important decision when photoreactions shall
be conducted. Ideally, the light source emits light with a wavelength identical to the wavelength
of the absorption maximum of the photochemical active species. In special cases it can also be
necessary to consider the absorption spectra of the product. This is required if the product also
absorbs light emitted by the light source and undergoes e.g. photodegradation or another con-
secutive photochemical reaction. Beside the emission spectra, the power of the light source de-
termines the performance of a photochemical reaction. Hence, if a high reaction rate is required,
a light source with a high optical power is necessary. In general, the luminescent efficiency of
artificial light sources is below 50 %, resulting in additional engineering demands if high power
light sources are used. Especially the heat generated by the light sources has to be removed by
an appropriate heat management. This is especially crucial if reactions are conducted, which are
temperature sensitive. It is evident that the characteristics of the light source dictate to a certain
extent the design of the photoreactor as well as the required periphery like temperature control
systems or safety measures.
In contradiction to the importance of the choice of the light source, only a low number of dif-
ferent light sources is available. In general light sources can be classified be the primary process
of light generation. Hence, thermal and non-thermal light sources can be distinguished. Ta-
ble 2.4 provides an overview of the different types of light sources and their typical application.
65
Table 2.4: Light sources and their properties.[25]
Mode of light Light Source Spectral Pel /W η max /% Application
generation Domain/nm
tungsten lamp 350 – 2 000 40 – 1 000 4 lighting
thermal
(incandescent lamp)
candles 300 – 2 000 – 200 6 lighting
halogen lamps 300 – 2 000 – 200 6 halogenation
xenon discharge 200 – 1 500 50 –30 000 10 industrial photoreactors
lamps
Hg low pressure 254 – 2 000 40 disinfection, polymerizations
lamps
Hg medium 250 – 600 – 60 000 40 disinfection, polymerizations, industrial
non thermal
pressure lamps photoreactors

Hg high pressure 250 – 600 – 60 000 45 industrial photoreactors
lamps
fluorescent lamps 254 – 700 10 – 150 25 polymerizations and reactions with high
quantum yields
Na low pressure 589 18 – 200 25 sensitized reactions
lamps

Na high pressure 450 – 750 50 – 10 000 15 sensitized reactions, lighting
lamps
Laser 157 – 3391 – 20 000 15 manufacturing, kinetic investigations
(organic) light 230 – 700 – 70 25 laboratory applications, lighting,
emitting diods electronics
66
·1013
4 5000 K
Intensity / W m-2 m-1

2
4000 K
3000 K
0
0 500 1000 1500 2000 2500 3000
λ / nm
Figure 2.59: Emission spectra of an ideal black body emitter for different temperatures.
2.3.1.2 Thermal Light Sources
Thermal light sources generate light by heating a material, e.g. a tungsten filament, causing a
thermal excitation of the electrons, consecutively relaxing to the ground state which is accom-
panied with the emission of a photon. Popular examples are incandescent lamps or candles. The
emission spectrum of thermal light sources is continuous and depends on the temperature of the
heated material. The distribution and the intensity of the emission can be described by Planck’s
law for an ideal black body emitter:
2πhc2 1
Mλ0 (λ , T )dAdλ = 5 hc
dAdλ . (2.58)
λ e λ kT ) − 1
(
The spectral irradiance Mλ0 is a function of the wavelength λ and the temperature T . It becomes
clear, that the main emission wavelength is shifted to shorter wavelengths as the temperature is
increased. This is illustrated in Figure 2.59. Because the black body radiation is only a function
of temperature, the maximum peak λmax can be calculated from Equation 2.58 as:
2.898 · 106 K nm
λmax = (2.59)
T
2.3.1.3 Non-Thermal Light Sources
For non-thermal light sources, the energy for exciting atoms or molecules is provided by a
non-thermal energy source. Among this group of light sources are discharge lamps, light emit-
67
0.8
0.6
Pλ / 1
0.4
0.2
0
300 400 500 600
λ/nm
Figure 2.60: Normalized emission spectra of a low pressure Hg lamp, a medium pressure Hg
lamp (gray), and a high pressure Hg lamp (dashed).
ting diodes and fluorescence lamps. Due to the quantization of the energy levels of atoms and
molecules, non-thermal lamps exhibit discontinuous spectra. With this the choice of the light
source for initiating photochemical reactions becomes even more important.
The most important light sources for driving chemical reactions are mercury arc lamps which
are available with different Hg pressures. Low pressures Hg lamps typically operate with a pres-
sure of 10 · 10−3 mbar to 10 mbar, medium pressure lamps with a pressure of over 1 bar and high
pressure lamps with a pressure of about 100 bar.[24] Table 2.5 gives an overview on the different
persistent spectral lines, which are emitted by mercury, and the corresponding energy levels.
Persistent in this case refers to emission lines, which are still measured with a minimal amount
of the investigated element. In spectroscopy these lines are of special importance because they
can be observed over a broad range of experimental conditions. The most dominant spectral
lines of Hg lamps are at 254 nm, 297 nm, 313 nm, 334 nm, 365 nm, 404 nm, 435 nm, 546 nm and
576 nm. In Figure 2.60 typical emission spectra for Hg lamps are shown as examples. While the
emission lines are very sharp for low and medium pressure lamps, the continuous fraction of the
spectrum increases with increasing operating pressure (line broadening). Due to this character-
istic, the spectral distribution characteristics of mercury lamps are often only represented by a
relative spectral distribution. With this, the emitted spectral power can only be calculated if the
optical power output of the light source is known.
68
Table 2.5: Persistent ultraviolet emission lines of mercury.[133]

Wavelength / Intensity / 1 Energy Levels / Configurations Terms
nm cm-1
0.00 5d10 (1 S)6s2 1S
253.56 100
54068.78 5d10 (1 S)6s6p 3 P◦
37645.08 5d10 (1 S)6s6p 3 P◦

296.73 25
71336.16 5d10 (1 S)6s6d (1/2, 3/2)
44042.98 5d10 (1 S)6s6p 3 P◦
365.02 60
71431.31 5d10 (1 S)6s6d (1/2, 5/2)
37645.08 5d10 (1 S)6s6p 3 P◦
404.66 40
62350.46 5d10 (1 S)6s7s 3S
39412.30 5d10 (1 S)6s6p 3 P◦

435.33 100
62350.46 5d10 (1 S)6s7s 3S
44042.98 5d10 (1 S)6s6p 3 P◦

546.07 50
62350.46 5d10 (1 S)6s7s 3S
Low pressure mercury arc lamps emit predominantly (80 %) at 253.7 nm, being the resonance
line of mercury. The higher pressure in medium and high pressure lamps causes the so called
autoabsorption phenomenon where the 253.7 nm emission band is absorbed by mercury atoms.
As a consequence, the 253.7 nm emission appears in the form of two lines separated by a narrow
dark zone, when the mercury pressure reaches 1 bar (inverted radiation).[134] Furthermore, the
higher Hg pressure as well as the higher temperature lead to excitation of the mercury atoms
to additional energy levels compared to low pressure lamps. This causes additional photon
emissions at longer wavelength. Tuning of the emission spectra can be achieved by adding
metal salts as dopants.[24]
Another way to produce UV radiation on a non-thermal way is the excimer emission. For
this purpose, gases are excited with accelerated electrons. The electrons are generated by an
electrode in the middle of the lamp and move to a second mesh electrode which wraps the
capacity filled with gas. Due to distinct excitated states, in most cases only one emission peak
with a narrow half width occurs.[135] The most common geometry for excimer lamps is tubular.
On their way, electrons excitate the gas molecules. Figure 2.61 shows the emission spectra
of three excimer lamps with emission in the UV-range. Xe∗2 excimer lamps emit light with a
peak wavelength of 172 nm, KrCl∗ excimer lamps with a peak wavelength of 222 nm and XeCl∗
excimer lamps with a peak wavelength of 308 nm. Due to the mentioned single and narrow
69
60
XeCl* excimer
KrCl* excimer
Pλ / W nm−1
Xe∗2 excimer
40
20
0
160 180 200 220 240 260 280 300 320
λ/nm
Figure 2.61: Emission spectra of a Xe∗2 excimer lamp a KrCl∗ excimer lamp a XeCl∗ excimer
lamp. Pel = 700 W.
emission, excimer lamps can be chosen for photochemical reactions where different reaction
pathways can be provoked with different wavelengths of the exciting light. For example, the
formation of an unwanted side product can be suppressed. On the other hand, light sources with
only one emission peak can only be used for some fitting reactions.
One of the newest light sources with one distinct emission peak are light emitting diodes
(LED). The functional principle is called electroluminescence and is shown in Figure 2.62. The
setup is similar to a pn-semiconductor diode. One big difference is the position of the energetic
levels and the band gaps. When an electron is transferred from the n- to the p-semiconductor,
it will fall from the conduction band to the valence band. This process can also be described
as the recombination of electrons and electron holes. The energy of the band gap between
conduction and valence band will be released as light. For a LED this amount of energy is in the
range of UV, visible and infrared light. As for other light sources, where the difference between
energy levels is used, the emission of LEDs possesses a narrow half width. In principle, a large
variety of wavelengths is possible by combining the appropriate semiconductors, however, the
efficiency of LEDs with different wavelengths still differs a lot and research is still in progress
for optimization.[136] The most efficient LEDs emit radiation between 365 nm to 465 nm. With
30 % to 50 % the efficiency is comparable to classical discharge lamps as Hg lamps or excimer
lamps. Figure 2.63 shows the emission spectra of several LEDs between 280 nm to 520 nm. To
70
E
photon emission
conduction band
electrons
valence band recombination

ΔE
holes
p-side n-side
Figure 2.62: Functional principle of a LED, showing the recombination of electrons and elec-
tron holes between the conduction and the valence band.
15
Pλ / W nm−1
10
0
300 350 400 450 500 550 600
λ/nm
Figure 2.63: Emission spectra of LEDs with the emission wavelengths of 365 nm, 385 nm, 395
nm, 405 nm, 450 nm, 465 nm and 520 nm. Pel = 700 W.
enable comparison of the intensity of the spectra in Figure 2.61, the electrical power Pel is scaled
to 700 W. LEDs emitting UV radiation below 350 nm show a much lower efficiency.
71
80
transmission / %
60
40
20
0
240 260 280 300 320 340 360 380 400 420 440 460 480 500 520
λ/nm
Figure 2.64: Overview of bandpass filters sold by the company Asahi Spectra.[137]
2.3.2 Optical Materials and Filter
Constructing photoreactors requires choosing a suitable construction material. Beside typical

constraints such as chemical or temperature resistance, special attention has to be paid to the
optical properties of the construction material. All materials between the light source and the
reaction zone have to be transparent for light with wavelengths required to drive the desired
reaction. This includes the reactor walls as well as cooling jackets (for both reactor and light
source).
Typically, some kind of glass is used. As long as wavelengths larger than approximately
300 nm are sufficient to initiate the reaction, borosilicate glasses can be used. The optical trans-
missions are well suited for this wavelength range. If shorter wavelengths are required, the
use of quartz glasses can not be bypassed. While this material transmits irradiation down to a
wavelength of approximately 170 nm and shows a very good chemical resistance, processing of
quartz is much more complicated compared to borosilicate glass. The more difficult processing
is the reason for much higher costs of quartz glass.
As explained in section 2.3.1 most technically used light sources emit polychromatic light,
from which usually only a certain wavelength range is beneficial for the desired reaction. Light
with other wavelength might induce undesired side reactions. Hence, it is required to prevent
light with undesired wavelengths from interacting with the reaction solution. This can be real-
ized by utilizing optical filters.
72
Optical filters can be solid or liquid materials. A wide variety of filter materials can be pur-
chased. Figure 2.64 shows an overview of the available filters for UV and visible light sold by
the company Asahi Spectra as examples. If solid filters such as colored glasses are used, it has
to be considered that the glasses will be heated by the absorption of the light which shall not
reach the reactor. Hence, it is necessary to provide sufficient cooling. The degree of absorption
of colored glasses often decreases during intense irradiation and a more frequent replacement of
the filter might be required during operation of the photoreactor.
As an alternative, filter solutions of inorganic salts and/or organic compounds can be used.
Circulating these solutions in the cooling system provides good heat management and an easy
replacement of degraded solutions. Combinations of different filters can be used to allow trans-
mission in small wavelength ranges only.
2.3.3 Reactor Types and Concepts
2.3.3.1 Conventional Reactor Types
The design of a photoreactor is determined by the geometric characteristics of the light source
to a large extent. Due to the fact, that the geometry of powerful light sources such as Hg va-
por lamps is often elongated, numerous reactor designs derivate from the general concept of
immersion reactors.
The general design of an immersion photoreactor is shown in Figure 2.65a. The light source
is centered in the middle of the reactor and surrounded by a cooling jacket. Depending on the
power and emission characteristics of the light source, an additional jacket might be required
to provide a sufficient thermal insulation or a liquid filter. The light source is immersed into
the reaction mixture. Depending on the reaction conditions, additional heat exchangers or static
mixing elements can be integrated into the reactor. In some cases it can be appropriate to “im-
merse” multiple lamps into the reaction mixture to adjust the ratio between irradiated surface
and volume of the reaction mixture. Considering the fundamental coherencies of absorption, it
reveals that the immersion reactor actually is not a well suited reactor type for photochemical
reactions. Because the rate of photochemical reactions depends on the rate of photon absorption,
it becomes clear that the reaction rate decreases with increasing optical path length. The reason
for its popularity for conducting photochemical reactions is the ease of use and set up.
A reactor type with a very high surface to volume ratio is the so called falling film reactor. By
use of different technical solutions, the reaction mixture is guided along the elongated dimension
of the light source as a thin film. Figure 2.65b shows an example of a simple falling film reactor.
The reaction mixture is pumped onto the inner wall of a glass jacket. The resulting falling film
is the dashed line in Figure 2.65b. The thickness of the falling film can be adjusted in a range of
73
liquid distributor
light source
falling film
coolant
light source
cooling finger
thermal insulation reaction reaction
cleaning
mixture mixture
reaction mixture
solvent for
cooling finger
(a) (b)
Figure 2.65: (a) Immersion photoreactor.[24] (b) Annular falling film photoreactor.[24]
light source
parabolic reflector
reaction mixture
Figure 2.66: Horizontal cross section of a schematic rayonet reactor.
several hundred µm by the physical properties of the fluid and the flow rate. In addition to the
large surface to volume ratio, which is favorable for reactions with high absorption, falling film
reactors can also be used beneficially for photochemical gas/liquid reactions. Due to the large
surface area and the good mixing, a very good gas/liquid mass transport can be achieved.
An alternative to immerse lamps into the reaction mixture is the possibility to surround the
reaction mixture with lamps. This can be done for example for weak absorbing compounds,
when a very high intensity of light is needed. This concept is applicable for a pipe, which is
74
flowed through continuously by the reaction mixture, or a flask, which is put into the center space
of the lamps (batch). The horizontal cross section of a so called rayonet setup is schematically
shown in Figure 2.66.
2.3.3.2 Microstructured Photoreactor
One important aspect of the design of photoreactors is the realization of a good irradiation of
the reactants. For this, the exponential decay of the light intensity caused by the interaction with
matter has to be considered. According to the B EER -L AMBERT-law (see section 2.1.3), a large
fraction of the light is already absorbed in a short distance from the reactor wall. Consequently,
it is possible that volumes in a large distance from the reactor wall are not irradiated. Such
not irradiated volumes are unfavorable due to two reasons: In these parts of the reactor, side
reactions can occur, which influence the selectivity of the photochemical process negatively.
Furthermore, photochemical reactions do not occur, in these regions, causing a decrease of the
overall performance of the reactor. In principle, this can be considered a wrong adaption of the
reactor to the process conditions. Such situations are frequently found in laboratories, because
the setup of the reactor and the light source can often not easily be adapted to the requirements
of the process conditions. An additional point might be the fact, that a reactor optimized to the
process conditions might not be required for laboratory purposes.
As an answer to the points raised above, the use of microstructures reactors became popular
during the last decade.[138–143] Microstructured reactors possess at least one reactor dimension
with a length of less than 1 mm. These short optical depths allow a good irradiation of the re-
action solution and with this an improved reaction control. Furthermore, conducting photoreac-
tions in microstructured reactors profits from the general advantages of microstructured devices.
Among others these advantages are the possibility of continuous processing and the possibility
to use miniaturized light sources, the improved heat and mass transport as well as the improved
process safety due to the low reactor volumes. Consequently, all relevant photochemical reac-
tion types have been successfully conducted in microstructured photoreactors. This includes
photosubstitutions, photoadditions, photoisomerizations, photorearrangements, photochemical
redox-reactions and photochemical cleavage. With this, it is possible to use the whole spec-
trum of photochemical reactions in microstructured reactors. This also applies to heterogeneous
reaction systems such as gas-liquid or gas-liquid-solid reactions.
The application of microstructured reactors is often referenced as flow chemistry. With re-
spect to photochemical reactions, this nomenclature falls short, because the possibility to utilize
continuous processing is only one aspect that makes this reactor type interesting for photochem-
istry. The combination of high-power light sources with short optical depths gives access to
75
operation conditions with very high intensities without the drawbacks of not irradiated volumes.
The continuous operation allows transformation of the time axis to a length axis and with this
it is possible to precisely adjust the reaction times. Hence, the degree of reaction control can
be increased. This point becomes even more relevant, when flow conditions are chosen, un-
der which the reactor shows plug flow behavior. In this case, the residence time distribution
is very narrow and consequently the reaction time distribution, too. Furthermore, back mixing
is minimized, what is beneficial for reaction networks with consecutive reactions. Consecu-
tive (photochemical) reactions can be quenched just after a certain selectivity threshold value
is reached. Most frequently, this will be the point where maximum selectivity is reached. Ad-
ditional benefits arise from the possibility to couple a continuously operated photoreactor to a
continuously operated downstream processing and/or online analytics. This combination allows
a further intensification of the overall photochemical process.
The simplest way of using microstructured reactors is the use of the capillaries with an inner
diameter of less than 1 mm. To conduct photochemical reactions, it has to be ensured, that the
reactor material is transparent to the light which is required to drive the reaction. Polymeric
capillaries, made of e.g., FEP or PFA can be used as well as capillaries made of glass or fused
silica. Glass capillaries have a better transparency, especially in the deep UV region but are more
difficult to handle due to the risk of breaking. Breakage is not an issue for polymeric capillaries,
which explains their frequent use in laboratories. Of course, this is only possible if the material is
transparent to the relevant wavelength region. Specialized microstructured photoreactors made
of glass, fused silica or combinations of transparent materials with metals for the reactor scaffold
are also commercially available.
Although, the performance of microstructured photoreactors is typically much better than that
of conventional photoreactors, the absolute output of a single microstructured reactor is compa-
rably low. Hence, concepts are required to achieve high absolute productivities. A classical scale
up of the reactors is impossible, because the benefits gained by microstructuring cannot be main-
tained on a microscopic scale. As a consequence, the concepts of scale-out and numbering-up
are used for microstructured reactors.
During a scale-out, all dimensions of the microstructured reactor are increased, which do not
contribute to the beneficial effects required to achieve a high performance.[144,145] For photore-
actors the optical depth is the most important parameter and should not be varied to a large extent
during scale-out. The two remaining dimensions are less critical and can be subject to scaling.
Numbering-up aimes on replicating the relevant structures several times. This can be done ex-
ternally, meaning that all parts, including pumps, periphery, the reactor, connecting tubes, etc.
are used several times. It is obvious, that this approach is simple, but associated with a large
investment. A more elegant way is internal numbering-up. For this, only the parts of the reactor,
76
which require microstructuring, are numbered up in a dedicated reactor housing and all other
parts are scaled up classically. Although, the design of the internally numbered-up reactor is
more challenging, the overall costs of the system, to realize a certain production, will be lower
than for external numbering-up.
2.3.4 Actinometry
2.3.4.1 General Information
The term actinometry refers to the measurement of the actinism, e.g. the photochemical effectiv-
ity of electromagnetic irradiation of different wavelength. According to that, an actinometer is a
chemical system or a physical device (e.g. a bolometer or photo cell) to determine the number
of photons in a light beam per time interval (photon flux) or integrally (amount of photons).[15]
Chemical actinometers are of particular interest due to a number of additional capabilities phys-
ical measurement methods do not offer. Hence, there is a lot of benefit in their use, even if
they are more challenging to handle and sometimes difficult to purchase or synthesize. The
advantages are namely:
• the physical condition of the probe solution can be adapted to the actual reaction compo-
nents including the photon interactions,
• the measurements are conducted right within the irradiated volume and thus include the
effects of transmission, reflection and scattering,
• for every experiment, the actinometer solution is freshly prepared and for that reason not
subject to age effects.
Especially the last point is an important feature and guarantees reproducible results for the de-
tected number of photons as the quantum yield for a given wavelength and concentration remains
constant. In contrast to that, the sensitivity of a commonly used silicon photodiode to photons
at a wavelength of 300 nm decreases by about 18 % per year, even without being in use.[146]
Depending on the state of matter, chemical actinometers can be classified into three groups:
• chemical actinometers in solid or a microheterogeneous phase,
• chemical actinometers in liquid phase,
• chemical actinometers in gaseous phase.
An overview of the most common systems is provided in a IUPAC Technical Report by K UHN
et al. [147] Besides general information about preparation and measurement methods, notes for
analytics and references for further reading are given.
Liquid chemical actinometers are suited best for an application in continuous setups because
a solid might clog the reactor and a gas is way less accurate to control. Nevertheless, there are
not many reports published in the literature. In fact, there are different approaches to create a
77
model of the conducted experiment[148] or the radiation characteristics of the light source[145] to
estimate the photon flux. In these modelings, the light source was assumed to be monochromatic
and the photon flux that theoretically reached the reaction solution was calculated for the irra-
diated volume. Alternatively, the information about the power distribution of the lamp provided
by the manufacturer can be used to calculate the received number of photons for each surface
element. But even a combination of both methods can only result in an approximate value be-
cause reflection, transmission of the reactor material and the alignment of the light source and
the reaction chamber are neglected.
In contrast to that, reliable conclusions on the efficiency and the optimization potential are
possible when chemical actinometry is conducted as the results can be directly linked to the
reactor geometry and the used construction materials.
2.3.4.2 The H ATCHARD-PARKER/Ferrioxalate Actinometer
One of the most commonly used actinometers is the liquid H ATCHARD-PARKER-actinometer

firstly presented and well-investigated in 1956.[149] The reaction system relies on the reduction
of Fe3+ in an oxalate complex to Fe2+ , responsible for its other common name: ferrioxalate
actinometer. The reaction is shown in Equation 2.60. Completing the redox reaction, one oxalate
ligand is oxidized to carbon dioxide and a carbon dioxide anion radical in Equation 2.61. The
latter may attack another ferrioxalate to a certain number, yielding in a second Fe2+ , formed out
of same absorbed photon as shown in Equation 2.62. This secondary reaction has a rather lower
probability to happen, but this way reaching an overall quantum yield Φ significantly higher
than 1 is possible.
hv
[FeIII (C2 O4 )3 ]3− GGGGGGA [FeII (C2 O4 )2 ]2− + (C2 O4 )·−
2 (2.60)
(C2 O4 )·− ·−
2 GGGGGGA CO2 + CO2 (2.61)
[FeIII (C2 O4 )3 ]3− + CO·−

2 GGGGGGA [Fe (C2 O4 )2 ]
II 2−
+ CO2 + (C2 O4 )2− (2.62)
In spite of the theoretical overall quantum yield of 2, a maximum of about 1.2 dependent
on the irradiated wavelength and the concentration of the actinometer solution was found by
H ATCHARD and PARKER in systematic experiments.[14] As references, the authors used the
uranyl oxalate actinometer and a radiation thermopile. Another focus of former studies lied on
the influence of the temperature coefficient on the quantum yield, but there was no detectable
dependency of the quantum yield from varying the temperature.[150]
78
In a final step to analyze the actinometer after the reaction (this step is called “development”),
an appropriate amount of 1,10-phenantroline in a buffered solution is added to quantitatively
give a strongly red complex with the photochemically formed FeII . This way, the concentration
can be easily determined via UV/VIS spectroscopy.
Over the past decades, some research groups adapted the experimental method and suggested
newly developed analytics.[151–154] But it is still a problem that due to the subsequent developing
process, no in-situ measurements (or at least measurements shortly after the irradiation process)
are possible with the ferrioxalate actinometer. Additional problems occur implicated by con-
tradictory recommended operating procedures ending up in different results. Hence, the results
should be verified thoroughly using a valid model and the corresponding calculations.[147]
2.3.4.3 Other Chemical Actinometers
Combining some other actinometers with reliable accuracy and reproducibility of the IUPAC
compilation, the spectral range between 130 nm to 750 nm can be investigated.[147] The most
convenient chemical actinometers are the uranyl oxalate photolysis (λ = 200 nm to 500 nm), the
azobenzene system undergoing an (E)-(Z)-isomerization between λ = 230 nm to 460 nm, the
photoisomerization of Aberchrome 540 under irradiation between λ = 310 nm to 375 nm and
the 7,16-diphenyldibenzo[a,o]perylene at wavelengths between λ = 475 nm to 610 nm. Thus,
complementary evaluations allow a defined characterization of a polychromatic light source in
relatively small spectral ranges.
2.3.5 Radiometry
Radiometry is the science of detection and measurement of electromagnetic radiation. This is

performed with the help of a radiometer. Central component of a radiometer is a photodetector.
The signal of such devices is a function of the intensity of the incident radiation. In most cases
the distribution in space or the received/emitted energy of the radiant energy is measured. In
photochemistry, radiometry is used to measure the radiation, which is available for a reaction, in
a photoreactor. This in turn is necessary for actinometry and the determination of the quantum
yield of a photochemical reaction.
The quantity giving information of the energy of a portion of radiation per time is the radiant
power P:
dQ
P= [P] = W. (2.63)
dt
For a radiant source it is the amount of energy Q per time t, which is emitted in every direction
as electromagnetic radiation. This quantity is wavelength dependent. Typical emission spectra
79
of light sources are shown in section 2.3.1. According to the IUPAC recommendations,[155] the
wavelength dependency of a quantity is indicated by a subscripted λ . Considering the entire
wavelength region requires integration within the respective wavelengths:
Zλ 2
x= xλ dλ . (2.64)
λ1
From the spectral radiant power Pλ it is also possible to determine the number of emitted pho-
tons. The energy can be calculated by the P LANCK -E INSTEIN relation (see Equation 2.1). With
this, the spectral amount of photons emitted per period qn,p,λ can be calculated from:
Pλ · λ
qn,p, λ = mol s−1 nm−1 ,

qn,p,λ = (2.65)
h · c · NA
As shown in Equation 2.64, the total photon flux results from integration:
Zλ 2
1 Pλ · λ
qn,p = mol s−1 .

qn,p = dλ (2.66)
h·c NA
λ1
It must be taken into account, that the number of photons per radiant energy is decreasing with
lower wavelengths. Especially when considering photochemical reactions, where the number of
photons is often relevant for the economy of the process. Hence, photon based quantities should
be used instead of energy based quantities when possible and meaningful. Figure 2.67 shows
the difference between energy and amount of photons as a function of the wavelength exemplary
for a theoretical monochromatic light source with Pλ = 1 W. Table 2.6 gives an overview of the
most common photon based and energy based radiometric units.
80
Table 2.6: Energy and photon based radiometric units in comparison to each other.
energy based photon based
name symbol unit name symbol unit
radiant power P W photon flux qn,p mol s−1

spectral radiant Pλ W nm−1 spectral photon qn,p,λ mol s−1 nm−1
power flux
irradiance E W cm−2 photon fluence En,p,o mol cm−2 s−1
rate
spectral irradiance Eλ W cm−2 nm−1 spectral photon En,p,o mol cm−2 s−1 nm−1
fluence rate
8 4
3.5
6
relative difference / 1
3
qn,p,λ / µmols−1
4 2.5
2
2
1.5
photon flux
relative difference
0 1
200 300 400 500 600 700 800
λ / nm
Figure 2.67: Photon flux of theoretical monochromatic light sources with a radiant power
Pλ = 1 W. Additionally, the relative difference to the photon flux at 200 nm is
given.
The amount of photons irradiated to a surface can be defined as photon fluence rate En,p,o :
qn,p
En,p,o = mol cm−2 s−1

En,p,o = (2.67)
Sirr
For point-shaped light sources it might be convenient to use the solid angle as reference quantity.
On a sphere with 1 m radius, a steradian covers a surface of 1 m2 (see Figure 2.68). The solid
angle of the entire sphere is 4π. Hence, the emitted radiant power (or photon flux) can be given
per unit solid angle Ω in a given direction:
dP
I= [I] = W sr−1 . (2.68)
dΩ
81
A
Ω= = 2π(1 − cos ϕ)
R2
Figure 2.68: Description of a steradian and the solid angle Ω.
Although ideal point-shaped light sources do not exist, this approximation is correct, if the
distance of the receiver towards the arc is 20 times greater than the arc. The use of a quantitiy
based on the solid angle can be useful, since it does not change with the distance to the light
source, only by the individual solid angle. Such a description can be beneficial for light sources
that do not have an isotropic light emission.
2.3.6 Reaction Engineering
Controlling photochemical reactions with the objective of high yields and high process efficiency
is more challenging as the same task for thermally initiated reactions.[24,25] This stems from the
requirement to consider the radiation field in addition to all parameters that are relevant for
conventional reactions. This leads to an increase of the number of variables relevant for reaction
control. Hence, reaction engineering of photochemical reactions is a challenging task. The
concerns raised on photochemical technology can be attributed to a large extent to this.
A typical sequence of points to be considered during the development of photochemical pro-
cesses is compiled in Figure 2.69. The prerequisite for a thorough design of such processes is
the knowledge of the reaction mechanism (or at least a reasonable hypothesis), the absorption
spectra of the relevant species and the solvent as well as the quantum yield of the reaction. The
emission spectrum of the light source has to be matched with this information. Subsequently, the
first design of the reactor geometry can be chosen, preferably under consideration of the geome-
try of the light source. For this first process design the (global) mass, radiation and heat balances
can be used to set up a mathematical model of the photochemical process. Under optimal condi-
tions, the B EER -L AMBERT-law can be used to describe the radiation field sufficiently detailed.
Depending on the complexity of the reactor geometry and therewith the positioning of the light
sources, modeling of the radiation field might be required to support modeling of the complete
process. By implementing the technological and economic constraints, a numerical solution can
be obtained that gives insights on the required reactor design, reactor operation, possibilities of
process optimization and scale-up. As for all numerical methods, the gained results have to be
validated against experimental data. As a consequence of the complex interactions involved as
82
reaction mechanism
reactor geometry
absorption spectra emission spectrum
and geometry of light source
quantum yield
mass balance
radiation balance
modeling of radiation field
heat balance
(momentum balance)
mathematical model technological and

of photochemical process economical constraints
numerical solution
reactor design reactor operation process optimization scale up
Figure 2.69: Reaction engineering aspects for photochemical processes.[25]
well as uncertainties in experimental or physicochemical data, an experimental verification of

the data predicted by the models might be required with an intermediate plant size.
For simple reactions, where irradiation of the reactant leads to excitation followed by reaction
of only this reactant, solutions for the above described balances can be obtained easily. This is
not the case for reactions that are only initiated by a photochemical step or where sensitization
drives the reaction. For processes using such photochemical reactions, mass transport effects
become relevant. For optimal process control it is required to minimize the impact of secondary
reactions that can become dominant in dark zones of the reactor. Hence, either mass transport
has to be intensified to such an extent that conditions equal to an ideally mixed tank reactor can
be assumed, or the reactor geometry has to be changed to avoid dark zones. For reactions where
radicals are involved, consideration of unwanted side reactions becomes even more important,
because the resulting byproducts can deposit at the reactor wall. This leads to a filter effect,
that increases with time. Consequently, reaction conditions, i.e. the photon flux received in the
reaction solution, change and process control is lost. It becomes clear, that sophisticated reaction
engineering is crucial for conducting photochemical processes efficiently.
83
2.3.7 Scale-Up Aspects of Photoreactors
When it comes to scale-up of photoreactors, several crucial aspects have to be considered. The
follwing remarks will give a short overview of relevant aspects of the scale-up rather than a
complete guide for scaling-up photochemical processes. In this section a well evaluated lab
a
scale photoreactor is assumed with a defined average volumetric rate of photon absorption Lp,V
(AVRPA), defined as the amount of absorbed photons per volume:
qn,p,λ · (1 − 10−ελ cd ) h i
a
Lp,V,λ = a
Lp,V,λ = mol s−1 m−3 nm−1 . (2.69)
Sirr · d
With a given absorption coefficient ε and a given concentration c of the reaction mixture, AVRPA
is specific to a certain reaction and the chosen setup. The AVRPA is the photochemical equiva-
lent to the time yield (STY). The only difference is that the actual chemical reaction is neglected.
This procedure is possible, because the photon flux and with this the technical characteristics of
the light source determine the rate of the reaction primarily. For continuous systems, the theo-
retical productivity and space time yield of the setup can be determined when the flow rate and
the quantum yield of the reaction are known.
When an increase of the production height is desired, the first point to check is, whether the
reactor is scalable. The central element of the reactor is the light source. The type of light
source directly determines the achievable increase in production. The popular medium or high
pressure Hg lamps can be purchased with an electrical power from 100 W up to 60 kW.[134] In
addition, the size of the Hg lamps scales linear with its power and the diameter of the emitting
arc and with that the diameter of the entire lamp changes little compared to the length of the
lamp. These technical characteristics can be related to the AVRPA. Because the emitted radiant
power scales with the length, what also applies for the irradiated surface, AVRPA does not
change significantly when more powerful Hg lamps are used. On the first sight, the scale-up
of photochemical processes using Hg lamps seems very simple. Nevertheless, this only applies
when neglecting all other aspects of a scale-up, e.g. heat management, mass transport, technical
feasibility, safety measures, and so on. At this point the classical scale-up problems associated
with a different scaling of surface and volume come into play. Consequently, challenges arise
for almost all “realistic” photochemical processes.
A perfect example underlining the complexity of a scale-up is the use of a Xenon arc lamp for
irradiation. The emitting arc has a length of only a few millimeters. Irrespective of the power
of the lamp, it will be a quasi punctual light source. Consequently, the irradiated surface of the
reactor will not scale that easy with the size of the lamp. It will be likely that the lamp will
over irradiate the reaction and probably, significant work has to be invested to design a process
84
yielding the desired quality of the product.

Another aspect is the operational mode of the reactor. In the last decade, microphotoreactors
gained a large amount of interest. The high surface to volume ratio is one reason for that.[156] In
addition, it is proclaimed, that a numbering-up instead of a scale-up is possible and reasonable
for microreactors, implying a simpler increase of production capacity. It is obvious, that the
overall costs for technical equipment will be larger than with for a “normal” scale-up, because
economy of scale does not apply anymore. Despite this, all reaction conditions are guaranteed
to remain constant and an increase of the production height can be achieved during a very short
period due to simple replication of the equipment.[157]
2.3.8 Industrial Preparative Photochemical Processes
The electrical energy used worldwide for photochemistry is estimated to several tens of megawatts.
Nevertheless, mainly due to industrial secrecy, very little information about industrial applica-
tions of photochemistry can be found in literature.
Due to the availability of Hg lamps with an electrical power of up to 100 kW, these are the
most frequently used light source for large scale applications. Excimer lamps only represent an
alternative for small plant sizes. However, when their use is technical feasible, these light sources
can be advantageous due to a quasi monochromatic emission. LEDs possess this advantage as
well, however, until now only application in surface treatment, e.g. film curing, became public.
Industrial photochemical applications can be classified into three parts: i) waste water treat-
ment and disinfection, ii) surface treatment and iii) preparative photochemistry. Photochemical
steps are used in waste water treatment for the complete oxidation and mineralization of organic
residues in combination with the use of H2 O2 or O3 /H2O2. These approaches have in common,
that hydroxyl radicals are produced as active species. Production of hydroxyl radicals can also
be achieved by the Fenton reaction. More detailed information can be found in section 2.3.9.
Plants of this type with an installed electrical power of up to 200 kW are known. For the dis-
infection of air, vacuum-ultraviolet radiation (λ < 200 nm) and TiO2 photocatalysis are used to
decompose pollutants. The objective of disinfection is the destruction or at least inactivation of
potential harmful microorganisms. Irradiation with hard UV light not essential causes the death
of the organism, but deactivation to prevent infections.
Surface treatment or coating curing processes are nowadays common in many industrial
branches like automotive or printing industries. UV-curing can be used to adjust the properties
of the coating, like durability or flexibility. As a consequence of the suited absorption character-
istics of the curing agents, this photochemical application is the first one with a widespread use
of UV-LEDs as light source. The demand for cured surfaces in most cases is limited to objects
85
with a size in the lower square meters, hence the size of the curing lamps is comparably small
to the lamps used in preparative photochemical processes. The technique of surface treatment
is well distributed over the world and applied in small industries as well. Thus, the electrical
power for photochemical surface treatment is hard to estimate.
Still, up to the present day in chemical industry thermally induced processes are mostly fa-
vored over photochemical pathways. This can not only be attributed to the high development
status or massive research in thermal processes, that often require the use of a catalyst. Instead,
some drawbacks of preparative photochemistry can be reasoned, which are still present. Most of
these disadvantages of preparative photochemical processes concern the utilized light source. As
mentioned above, in industry mainly Hg lamps are used. Such emitters usually have a low elec-
trical efficiency. In the worst case up to 90 % of the applied electrical energy are transformed to
waste heat, making expensive cooling devices necessary. Furthermore, the polychromatic emis-
sion spectrum of Hg lamps can induce side reactions. Consequently, this has to be avoided by
the use of filters, which leads to additional expenses.[14,15]
Nevertheless, there are some crucial points that make preparative photochemistry attractive for
industrial applications. By using photochemical synthetic pathways the number of process steps
can be reduced significantly. Often, purification steps, which are necessary for most thermal
processes, can be omitted. This is a direct consequence of high selectivities, that can be achieved
by optimal reaction control. Additionally, some chemical end products are even only accessible
through photochemical synthetic ways.[15]
The economy of a photochemical process for industrial application depends on multiple fac-
tors. A main parameter is the quantum yield Φ of the applied photochemical reaction. With
information about this reaction property, it is possible to calculate the costs arising from the
required electrical energy. The amount of the desired product n produced per energy can be esti-
mated with Equation 2.70 when a monochromatic irradiation is assumed as first approximation:
n = 0.0302 mol kW−1 h−1 λ · η · Φ · f (2.70)
λ is the emitted wavelength in nm. η is the power-to-light efficiency at this wavelength. Φ is

the quantum yield of the photoreaction. f is the fraction of light absorbed by the product. The
prefactor can be derived from the P LANCK -E INSTEIN correlation (see Equation 2.1) when the
amount of photons per kW h is calculated.[14]
To assess the economic efficiency of a photochemical industrial process, it has to be checked
if the quantum yield of the reaction is above or below 1. In this context, photoreactions with
quantum yields Φ 1 (e.g. radical chain reactions) are favored for industrial use. For such
reactions the number of induced reaction steps per absorbed photon is very high. The accruing
86
energy costs for the operation of the light source have very low influence on the total production
costs. When the reaction quantum yield is below 1, the inverse is true. In this case the light
source efficiency η becomes the crucial parameter for the economy of the process.[14]
The absorption factor f can be deduced from the Beer-Lambert-law (see Equation 2.3). For
reactants with large extinction coefficients, low concentrated solutions, which are irradiated in
reactors with small depths, are favorable. On an industrial scale this is only achieved in thin-
film/falling film reactors that have a lower space-time-yield compared to conventional photore-
actors. Furthermore, low concentrations demand higher amounts of solvent. This directly affects
the process efficiency due to the additional steps required for solvent recycling.[14] In practice, a
compromise between the technically realizable layer depth and the possible reactor performance
has to be made. For reactants with small absorption coefficients, a batch reactor with large opti-
cal depths can be appropriate. In contrast, for reactants possessing large absorption coefficients,
reaction control is only maintained when the optical depth is sufficiently small.
In addition to theses factors, some practical aspects have to be considered. The purity of
the reactants and solvents must be high enough to avoid unwanted light extinction as well as
quenching of photochemical processes. Furthermore, precipitation of product or side products
on the light source has to be prevented.[14]
Several photoreactions introduced in this document are conducted on an industrial scale by
various, companies such as Philips, Bayer or BASF. Prominent examples are photochlorination
and photonitrosylation. A detailed description of these reactions can be found in the particular
chapters.
2.3.9 Waste Water Treatment
Waste water can be defined as water, which was contaminated by domestic, agricultural or in-
dustrial use. Typically, a distinction is drawn between waste water from private and commercial
or industrial use.[158] From domestic use waste water usually results from washing processes or
sanitary use. Typical contaminations are detergents or feces.
Industrial waste water was used for raw material extraction, as solvent or reaction substrate
or as cooling medium. Thereby cooling water is the principal part of industrial waste water.
The contamination may vary strongly and the contaminats can be differentiated according to
following groups:[158]
• dissolved or undissolved substances,
• readily degradable or persistent substances,
• herbal nutrients, heavy metal compounds or salts.
87
Figure 2.70: Scheme of the section for mechanical waste water treatment.[158]
To protect bodies of water, rivers and lakes from contamination, waste water has to be treated to
remove pollutants as far as possible. In general, waste water treatment can be subdivided into 3
general procedures.
• Mechanical waste water treatment is used for a first rough separation of pollutants such as
fabric residues, pieces of wood, plastic objects, feces and sand. For that, rakes, filters and
sedimentation basins are used.
• Biological waste water treatment implies a more advanced purification because dissolved
pollutants are degraded as well. Microorganisms degrade the contaminants. Organic com-
pounds are degraded through aerobic and non-aerobic processes. In this way, inorganic
compounds and biomass are released as degradation products. It is important to note, that
microorganisms have to be protected against acidic and basic solutions and diverse tox-
ics. Hence, thorough upstream processing of the waste water is crucial for operation of
biological waste water treatment.
• Chemical waste water treatment includes the use of chemical substances for procedures
such as precipitations, neutralizations and flocculations. The objective of such procedures
is the conversion of dissolved substances into insoluble compounds, which can be easily
removed afterwards by mechanical treatment processes.[158]
The design of a waste water treatment plant is strictly oriented by this general procedures. Un-
treated waste water is pumped into a basin containing a rake for mechanical treatment first.
Major pollutants are removed, collected and afterwards burned in a waste combustion plant. Af-
ter this, the water is pumped into a downstream basin containing an oil- and sandfilter. Oils,
fats and sand are separated from the waste water and pumped into the digestion tank (see Fig-
ure 2.70).[158,159]
In the second section of a waste water treatment plant, waste water is biologically processed
by pumping the water into an aerated basin containing a so called bacteria sludge. The air supply
enables the degradation of carbon, nitrogen and phosphorus compounds by aerobic processes.
At this stage, the water is almost purified. A downstream secondary sedimentation tank ensures
the separation of the aggregated and sedimented bacteria. This sludge is either pumped into the
88
Figure 2.71: Scheme of the section for biological waste water treatment.[158]
Figure 2.72: Scheme of the section for chemical waste water treatment.[158]
digestion tank or back into the air supply basin. A scheme of the biological section of a waste
water treatment plant is shown in Figure 2.71.[158,159]
As mentioned above, chemical treatment represents the last step of waste water treatment. In
multiple basins heavy metals, phosphates and nitrates are removed through precipitation. After
this step, the water is pumped into adjacent waterbodies. The sewage sludge can be collected in
the digestion tanks. In these tanks anaerobic fermentation occurs. The released methane can be
used to generate electric energy and the solid residue can be utilized as fertilizer or, depending
on its contamination, burned in a power plant.[158,159]
2.3.9.2 Contamination of Waste Water with Pharmaceuticals
Pharmaceuticals are one of the main products of European chemical industry with a share of
25 %. The pharmaceutical industry in Germany produces about 30 000 t of pharmaceuticals
per year. Pharmaceuticals are usually very stable chemical compounds. Besides ensuring high
activity, it is a crucial objective in pharmaceutical research to guarantee a long term stability of
distinct products. In this way, it is ensured that some drugs such as Diclofenac deploy their full
efficacy in the bowel by protruding gastric acid. On this account, most pharmaceuticals are dis-
charged unchanged. Because waste water plants are not constructed for degradation of dissolved
persistent chemical compounds, most pharmaceuticals are not removed during the treatment of
municipal or industrial waste water and are released to natural water bodies. In recent years,
it has been shown that this increasingly becomes a serious problem for the environment and
89
mankind. An indicator for this is the growing accumulation of more than 180 of the 3000 ac-
credited drugs in water bodies, that can already be observed today. Hence, the accumulation of
popular drugs such as Diclofenac is subject to recent research with the objective of a decrease
of the amount released to nature.[160]
70 % of the ingested amount of Diclofenac remains unchanged and is egested by the human
body. In Germany the annual consumption of Diclofenac reaches 90 t. The maximum allowed
concentration of Diclofenac in water bodies in Germany is 0.05 µg l according to legislation. In
several German regions this value is exceeded. In recent studies it could be shown that trouts
exposed to this Diclofenac concentration revealed multiple harms to animal skin, kidney or
branchia.[160]
In future, pharmaceutical degradation will become an important task in waste water treatment.
In this context, application of Advanced Oxidation Processes in waste water treatment represent
an approach to handle this problem.
2.3.9.3 Advanced Oxidation Processes
Advanced Oxidation Processes are distinct processing methods that make use of the formation
of hydroxyl radicals •OH. Hydroxyl radicals are a highly reactive, non-selective species with
a lifetime in the µs-range. •OH radicals are strong oxidation agents that react even with very
stable chemical compounds. Hence, •OH radicals are suited as reagent for degradation reactions.
Although all AOPs make use of the same reactive species, generation of the radicals can be
achieved differently. Popular AOPs are the Fenton-process using H2 O2 together with Fe2+ and
photocatalytic methods using TiO2 and UV-light.[161]
2.3.9.4 Fenton Reaction and Photo-Fenton-Process
The Fenton reaction yields hydroxyl radicals from the reaction of Fe2+ with H2 O2 . The Fe2+ ion
is oxidized to Fe3+ and hydrogen peroxide dissociates to a hydroxyl radical •OH and a hydroxyl
anion OH – . Subsequently, Fe3+ reacts with hydrogen peroxide to Fe2+ , forming HO•2 radicals.
These radicals can reduce Fe3+ again. H2 O2 reacts with hydroxyl radicals to H2 O and HO•2
90
radicals.[162]
Fe2+ + H2 O2 GGGGGGA Fe3+ + OH− + •OH (2.71)
Fe3+ + H2 O2 GGGGGGA Fe2+ + HO2 • + H+ (2.72)
Fe3+ + HO2 • GGGGGGA Fe2+ + O2 + H+ (2.73)

•
OH + H2 O2 GGGGGGA H2 O + HO2 • (2.74)
Hydroxyl radicals can be generated by irradiation with UV-light as well. The combination of
the Fenton reaction with irradiation is called photo-Fenton-reaction. Combining two different
initiation steps provides high local •OH concentrations and with this high reaction rates. This is
ensured by two ways: Firstly, by photochemical reduction of Fe3+ and secondly by homolytic
cleavage of H2 O2 .[162]
hv
Fe3+ + H2 O GGGGGGA Fe2+ + OH• + H+ (2.75)
hv
H2 O2 GGGGGGA 2 OH• (2.76)
Fenton and photo-Fenton-reactions have to be operated at pH values of 3 to provide optimal

conditions for hydroxyl radical formation. Above this value precipitation of Fe3+ ions occurs.
Below a pH value of 3, H+ ions react with hydroxyl radicals under formation of water. Both
reactions decrease the efficiency of the overall degradation process.[162,163]
2.3.9.5 Photocatalytic Processes
AOPs using photocatalysts are very attractive options for the mineralization of dissolved phar-
maceuticals in waste water. Usually metal oxides and especially semiconductors such as TiO2
are used for this purpose. TiO2 is the most prominent photocatalyst, because it is a cheap, pH
stable compound with a high photocatalytic activity. Usually TiO2 P25 from Evonik is used as a
suspension. This is a white powder with an average particle size of 21 nm and a specific surface
of 50 m2 g−1 . It consists of Anatas (70 %) and Rutil (70 %).[164,165]
hv
TiO2 GGGGGGA TiO2 (ecb − + (hvb + ) (2.77)
hv
H2 O2 GGGGGGA 2 OH• (2.78)
91
During the photocatalytic process electrons are excited from valence band to conduction band
by absorption of UV light. In this way an electron hole in the valence band and a highly reactive
and mobile electron in the conduction band are formed. Via oxidation of adsorbed H2 O and
OH – molecules by the electron hole hydroxyl radicals are generated. Meanwhile, oxygen is
reduced by electrons in the conduction band to superoxide radical.[164,165]
TiO2 (hvb + ) + H2 Oad GGGA TiO2 + OHad • + H+ (2.79)
TiO2 (hvb + ) + OH−

ad GGGA TiO2 + OHad
•
(2.80)
TiO2 (ecb − ) + O2 GGGA TiO2 + O2 •− (2.81)
This radical can react with a nearby proton to form a perhydroxylradical. Two perhydroxylradi-
cals can combine to oxygen and hydrogen peroxide. Finally, hydrogen peroxide can be reduced
to one hydroxyl radical and one hydroxyl anion.[166] Equation 2.82 to 2.84 illustrate the single
reactions.
O2 •− + H+ GGGA HO2 • (2.82)
2 HO2 • GGGA H2 O2 + O2 (2.83)
TiO2 (ecb − ) + H2 O2 GGGA TiO2 + OH• + OH− (2.84)
92
Practical Part
3
3.1 Photoreactions in the Laboratory Course of Technical
Chemistry
3.1.1 General Information
The laboratory course of Technical Chemistry is an obligatory part of the chemistry studies in
the 5th semester as a part of the Bachelor grade. It consists of six different experiments to get
basic knowledge on mechanical and thermal unit operations as well as reaction engineering.
The students carry out the experiments by themselves under the supervision of an assistant after
passing the introductory colloquy to check their preceding preparation. After the experiments,
the students have to write a protocol, in which they have to answer several specific questions.
The experiment referring to photochemistry is dedicated to the investigation and evaluation
of two different photoreactor types. Mercury vapor lamps with different power are used as light
sources to drive the reaction. The same lamp type was chosen for both reactor setups to exclude
differences in the emission spectrum. Hence, only the power of the light source and the reactor
setup influence the photon flux received in the reactor. Using the example of the degradation
of rose bengal, a falling film photoreactor (see Figure 3.1a) and a microphotoreactor (see Fig-
ure 3.2) are operated in three consecutive runs with different flow rates. The concentration of
rose bengal is measured by UV/VIS spectrometry during the experiment. Measurements for the
microreactor are conducted in a flow through cell and for the falling film reactor a cuvette is
used for the subsequently taken samples (see Figure 3.1b). Both reactor types are characterized
in terms of reaction engineering aspects. This includes handling of figures of merit for reactor
characterization like productivity and space time yield. Additionally to such general numbers,
the features of photochemical reactors are evaluated. In this context, the energy efficiency and
the external photon efficiency are introduced. The energy efficiency ξel is defined as the ratio
3.1 Photoreactions in the Laboratory Course of Technical Chemistry
(a) (b)
Figure 3.1: (a) Falling film reactor; (b) top: spectrometer, bottom: light source for both spec-
trometers.
of the change of molar flow of the product before and after the irradiation ṅout in
P − ṅP and the
electrical power Pel consumed by the lamp:
ṅout in
P − ṅP
ξel = . (3.1)
Pel
Therefore, the unit of the electrical efficiency is mol J−1 . The other characteristic factor men-
tioned is the external photon efficiency. This number transfers the characterization to the photon
level by comparing the molar product flow with the emitted photon flux of the light source ṅem :
ṅout
P − ṅP
in
ξext = . (3.2)
ṅem
The external photon efficiency is a dimensionless number.
94
(a) (b)
Figure 3.2: (a) Setup of the whole apparatus of the UV-Cube; (b) the micro reactor plate.
A well-grounded interpretation of the experimental results including a comparison of both

reactor types is expected in the protocol to show the gained knowledge of the students. Fur-
thermore, the students become familiar with transferring the figures of merit to other reactor
conditions by estimating the effect of different operation parameters and methods.
3.1.2 Experimental Procedure
The degradation of rose bengal (Figure 3.3a) is investigated in two different reactor types: a
falling film photoreactor and a microstructured photoreactor. Both setups are available from
Peschl Ultraviolet GmbH, Mainz, Germany and feature medium pressure mercury lamps with
700 W and 150 W, respectively. The solution containing rose bengal will be cycled between
the reactor and a reservoir vessel in both setups. Concentration measurements are conducted
with two spectrometers and a UV/VIS lamp from Avantes BV, The Netherlands. The absorption
spectrum at the beginning of the reaction is shown in Figure 3.3b.
Two different reaction solution with concentrations of 20 µM (V = 1 L) and 5 µM (V = 25 mL)
are required for the experiments and have to be prepared first. The 20 µM solution will be used
for the falling film reactor and the 5 µM solution for the microstructured reactor.
95
1.5
A/1
0.5
0
200 300 400 500 600
λ/nm
(a) (b)
Figure 3.3: (a) Chemical structure of rose bengal and (b) its absorption spectrum.
3.1.2.1 Preparation of the Spectrometer
The transmission of the reaction solution will be followed at a wavelength of 540 nm. A flow
through cell will be used for monitoring the concentration in the microstructured reactor. The
concentrations in the falling film reactor are followed by sampling and consecutive measurement
of the solution in a cuvette. For this, the following steps are required for both cells to prepare
the analytic method for the experiments:
1. Turn on both lamps (deuterium and halogen lamp) of the UV/VIS light source at least 15
min before the first measurements or saving the reference spectrum to allow the lamps to
stabilize. The TTL-switch should be switched to “off”. Both lamps must not switched off
during the experiments. Only the TTL-switch should be used to control the illumination
of the cells.
2. Start the program “AvaSoft8” from the desktop.
3. Choose the measure mode scope “S”. Save a dark spectrum before switching on the
TTL-switch by clicking on the “Dark” button.
4. Put a cuvette filled with purified water in the cuvette holder and rinse the flow through cell
with purified water.
5. Save the reference spectrum for both cells by clicking the “Reference” button.
6. Change to measure mode transmission by clicking on “T”.
Therewith, both UV/VIS cells are prepared for the measurements and should show 100 % trans-
mission in both spectra.
96
3.1.2.2 UV/VIS Measurements
The spectra of the initial reaction solutions have to be recorded first. For this, the microstructured
photoreactor is rinsed with the 5 µM reaction solution and the cuvette is filled with the 20 µM
solution. The cuvette must be placed in the cuvette holder. The spectra are recorded in single
mode by clicking the “Start” button and saved in folder “Experiments”. As a guide for the eyes,
these spectra can be displayed during the experiments by opening the respective tab.
Repetitive measurements after a given time can be automatically measured by the software.
Therefore, the mode “TimeSeries” has to be chosen first. This opens a new tab. To enable
simultaneous measurements for both reactors, two tabs are required. The routines for repeti-
tive measurements are saved as functions “fallfilm_peak_540” and “mikro_peak_540”. One of
these functions has to be loaded in one of the tabs. The routines measure the transmission at a
wavelength of 540 nm every minute for the microstructured reactor and every 10 minutes for the
falling film reactor. To enable correct measurements in the cuvette, the cuvette has to be filled
with a current sample every 10 minutes manually. Wearing suited safety glasses is mandatory
during sampling! The measurements are started by clicking on the “Start” button. The results
are exported to an Excel sheet after the measurements are stopped by clicking the “Stop” button.
3.1.2.3 Reactor Startup
At the beginning of the course day, the circulating thermostat has to be switched on. The cooling
water temperature has to be set to 20 ◦C. The cooling water tubes have to be checked for leaks
and a sufficient cooling water flow rate in the UV-Cube, the reactor plate and the falling film
reactor. When no leaks are detected, the pumps can be turned on and the given flow rates can
be set.
Only after the pumps are running, the mercury vapor lamps are switched on by the assistant.
The following flow rates have to be investigated:
• microstructured reactor: 0.5 mL min−1 , 0.75 mL min−1 and 1 mL min−1
• falling film reactor: 240 mL min−1 , 360 mL min−1 and 480 mL min−1
3.1.3 Evaluation of Experimental Data
Based on the experimental data (time resolved transmission values) gathered, the following fig-
ures of merit should be calculated for all process conditions investigated:
• conversion,
• space-time-conversion (equals the space-time-yield, but based on conversion)
• productivity,
• energy efficiency.
97
It should be discussed, which parameter is influenced by which change of the process conditions.
With these numbers at hand, the results should be compared and the investigated reactors
as well as the different process conditions should be characterized. What conclusions can be
drawn from the results? The compiled graphs should be discussed with respect to the different
coherences of the falling film and the microstructured reactor. What behavior of the curves can
be expected for longer reaction times?
The influence of different mode of operation (batch, semi-batch, continuous) on the calcu-
lated figures of merit should be estimated based on the experience made with thermally initiated
reactions. What reaction conditions should be chosen for which mode of operation? Do other
relevant parameters exist, which influence the choice of the mode of operation?
3.1.3.1 List of Equipment
The following equipment is used in this experiment:

• two medium pressure mercury lamps (700 W and 150 W) including the power supply
units,
• a circulating thermostat with an automatic alarm,
• a PMMA-shielded falling film reactor system and a microreactor system, both from Peschl
Ultraviolet,
• a peristaltic (falling film) and an Ismatec rotary piston pump (microreactor),
• a flow through cell and a cuvette in a cuvette holder connected to an Avantes spectrometer
and the Avantes light source with two connections,
• a desktop computer with installed Avantes software to measure and save the spectra,
• UV-light suited safety glasses for each student.
98
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Introduction to Photochemical

Reactions and Processes

Stuttgart, May 19, 2017

2.2.4 BARTON Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

2.3.7 Scale-Up Aspects of Photoreactors . . . . . . . . . . . . . . . . . . . . 84

2.1.1 Electromagnetic Radiation

Table 2.1: Classes of electromagnetic radiation and the caused interaction.

200 300 400 500 600 700

2.1.2 Wave–Particle Duality

2.1.3 B EER -L AMBERT-Law

2.1.4 Models of Chemical Bonds

2.1.4.1 Molecular Orbital Theory

A fundamental knowledge of the electronic states in molecules or complexes is the foundation

s px py pz dxy dxz dyz dx2 −y2 dz2

Figure 2.3: Different atomic orbitals.

(a) (b) (c)

Figure 2.5: MO schemes of (a) O2 and (b) CN – molecule.[8]

2.1.4.2 Ligand Field Theory

dxy dxz dyz

dx2 −y2 dz2

Figure 2.6: Octahedral coordination of d-orbitals.

Tetrahedaral Complexes For complexes showing a tetrahedral coordination the situation is

isolated ion spherical coordinated octahedral coordinated

Figure 2.7: Ligand field scheme of an octahedral complex.

dxy dxz dyz

dx2 −y2 dz2

Figure 2.8: Tetrahedral coordination of d-orbitals.

isolated ion spherical coordinated tetrahedral coordinated

Figure 2.9: Ligand field scheme of a tetrahedral complex.

I− <Cl− <F− <OH− <H2 O<NH3 <CN− ≈ CO.

Mn2+ <Ni2+ <Co2+ <Fe2+ <V2+ <Fe3+ <Cr3+ <V3+ <Co3+

2.1.5 Interaction of Light with Chemical Bonds

2.1.5.1 General Considerations

2.1.5.2 Energy of Photons

2.1.5.3 F RANCK -C ONDON Principle

2.1.5.4 J ABLONSKI Diagram

2.1.6 Relations Between Chemical Structure and Electron Spectra

metal orbital molecular orbital ligand orbital

2.1.7 W OODWARD -H OFFMANN Rules

Figure 2.14: Influence of different configurations and substituents on absorption behaviour of

approach to explain differences between thermal and photochemical electrocyclic reactions by

Figure 2.17: Orientations of suprafacial and antrafacial processes.[16]

Figure 2.18: Reaction of 1,3-Butadiene with ethylen.[16]

2.2 Reaction Types

2.2.1.1 General Concept

2.2.1.2 [4+2]-Cycloadditions (D IELS -A LDER-Reactions)

[4+2]-cycloadditions (D IELS -A LDER-reactions) represent the prototype of cycloadditions of the

Figure 2.19: Reaction of 1,3-Butadiene with maleic acid dimethyl ester.[18]

Figure 2.20: General reaction mechanism of Paternò-Büchi reaction.

H3C CH3 H3C CH3

2.2.2 Photooxygenations and S CHENCK-En-Reactions

H2 O2 + ClO− −−→ H2 O + Cl− + 1O2 , (2.7)

Bengalrosa Methylen Blau

Figure 2.25: Excitation of an ketone and formation of the biradical.

2.2.3 N ORRISH Type I and Type II Reactions

2.2.3.1 Norrish Type I Reactions

Figure 2.28: Synthesis of anti aromatic cyclobutadiene.

2.2.3.2 Norrish Type II Reactions

Norrish type II reactions are characterized by formation of a biradical through intramolecu-

Figure 2.29: Norrish type II reaction mechanism.

Laserphotolysis experiments showed that the lifetime of biradicals is in the range of 30 ns

2.2.3.3 Norrish Type I Reactions vs. Norrish Type II Reactions

2.2.4 BARTON Reaction