NJC

View Article Online

PAPER View Journal | View Issue
Published on 25 November 2013. Downloaded by St. Petersburg State University on 07/02/2014 03:11:41.

Synthesis and crystal structures of a series

of Schiff bases: a photo-, solvato- and
Cite this: New J. Chem., 2014,
38, 730 acidochromic compound†
Arturo Jiménez-Sánchez,a Mario Rodrı́guez,*b Rémi Métivier,c Gabriel Ramos-Ortı́z,b
Jose Luis Maldonado,b Netzahualcoyotl Réboles,b Norberto Farfán,d Keitaro Nakatanic
and Rosa Santillan*a

Seven Schiff base derivatives of 4-dimethylamino-trans-cinnamaldehyde were synthesized in good yield.

Received (in Porto Alegre, Brazil)
6th August 2013,
Accepted 25th November 2013
DOI: 10.1039/c3nj00895a
www.rsc.org/njc
The structures of all new derivatives were established by IR, 1H, 13C NMR and HRMS experiments and
three of them were corroborated by X-ray diffraction studies. Analysis of the supramolecular structures
evidenced the presence of strong intermolecular hydrogen bonds (O–H  N) which promote the
formation of molecular chains. The linear properties of this series of chromophores were investigated by
UV-Vis and fluorescence spectroscopy in solution and in the solid state. The results revealed interesting
photochromic properties for compound 2a promoted by a hydrogen bonding interaction in the solid
state, which was established by absorption and emission spectra. Further evidence of the specific
interactions that take place in compound 2a was obtained by studying the solvent effects observing a
solvato- and acidochromic behavior.

Introduction
Schiff bases are common organic structures which can be easily
synthesized through a one-step synthetic procedure via con-
densation of aldehydes with aromatic or aliphatic amines.1 For
years, Schiff bases have been widely used as toxic and essential
metal sensors,2 as molecular memory devices and switches,3
in non-linear devices,4 as catalysts,5 in electrochemistry and
magnetochemistry,6 in asymmetric synthesis and epoxidation,7
in biomedical applications8 and they have also been used
extensively as ligands in coordination chemistry.1 Many aromatic
Schiff bases exhibit the tautomeric equilibrium (N  H–O 2
N–H  O, enolimine 2 ketoenamine forms) which is pro-
moted by intramolecular or intermolecular proton transfer
a
Departamento de Quı́mica, Centro de Investigación y de Estudios Avanzados del IPN,
CINVESTAV, Apdo., Postal 14-740, México, D. F., 07000, México.
E-mail: rsantill@cinvestav.mx; Fax: +52-555-747-3389; Tel: +52-555-747-3725
b
Centro de Investigaciones en Óptica, CIO, Apdo., Postal 1-948, 37000 León Gto,
México. E-mail: mrodri@cio.mx
c
Laboratoire de Photophysique et Photochimie Supramoléculaires (UMR 8531 du CNRS),
Ecole Normale Supérieure de Cachan, Avenue du Président Wilson, 94235,
Cachan, France
d
Facultad de Quı́mica, Departamento de Quı́mica Orgánica,
Universidad Nacional Autónoma de México, D. F., 04510, México
† Electronic supplementary information (ESI) available: NMR characterization
and experimental procedures. CCDC 953089 (2a), 953090 (1b), and 953091 (1c).
For ESI and crystallographic data in CIF or other electronic format, see DOI:
10.1039/c3nj00895a
between the hydroxyl oxygen (O–H) and the imino nitrogen
atoms (RCQNR). Several studies have shown that this process is
responsible for the photochromic or thermochromic properties
observed in the solid and solution states for imine derivatives of
salicylaldehyde.9
Moreover, Schiff bases exhibiting photochromism10 are of
current interest due to their potential applications in single
molecule photochromism,11 optical switching devices12 and
data storage devices.13 In this regard, salicylidene-aniline deri-
vatives (SA) have been the most studied compounds while those
of cinnamaldehyde are less common.14
In the development of molecular photonic devices, the
combination of properties resulting from the interaction with
light is an important target for the design of bi- and multi-
functional fluorescent probes15 which can avoid the usage
of several probes and difficulties like cross-talk.16 Then, it is
interesting to design molecules exhibiting solvatochromic behavior
which can synergistically respond to the media.17
Previous results on derivatives of enolimines exhibiting
photochromic18 and solvatochromic19 properties have shown
that the stabilization of ketoenamine tautomers can be attri-
buted to a strong intermolecular proton transfer. With regard
to cinnamaldimines, we have reported the evaluation of the
non-linear optical properties as the first and second hyper-
polarizabilities of several derivatives.20
In continuation with our studies of the role of hydrogen bonding
interaction in the supramolecular structure of Schiff bases,

730 | New J. Chem., 2014, 38, 730--738 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2014

Paper
Published on 25 November 2013. Downloaded by St. Petersburg State University on 07/02/2014 03:11:41.
Scheme 1 Synthesis of compounds 1a–1d and 2a–2c.
we report a set of seven derivatives synthesized through conden-
sation reaction between 4-dimethylamino-trans-cinnamaldehyde
and the corresponding aromatic or aliphatic aminoalcohol as
shown in Scheme 1.
Analysis of the X-ray structures allowed exploring the direc-
tional recognition between the OH group and the imino nitrogen
atom, and its role in the photochromic properties. Although
compounds 1b, 1c and 2a exhibit hydrogen bonding inter-
actions, only compound 2a presented photochromism in the
solid state attributed to an intermolecular proton transfer.
In addition, we studied the solvatochromic behavior of 2a in order
to explore the solvent effect on the proton transfer interactions in
solution. Finally, with the purpose of studying the origin of the
involved electronic transitions, we calculated Frontier Molecular
Orbitals (FMOs) and electronic excitation parameters by means of
DFT and TD-DFT/PCM, respectively.
Experimental
Materials and physical measurements
Starting materials and solvents were commercially available
and used without further purification. Infrared spectra were
obtained on a FTIR Varian Spectrometer ATR.
Melting points were measured on an Electrothermal 9200
apparatus. 1H and 13C NMR spectra, homonuclear 1H–1H COSY
and heteronuclear 1H–13C HETCOR correlation spectra were
recorded on a JEOL eclipse ECA +500 spectrometer. Chemical shifts
(ppm) are relative to (CH3)4Si for 1H and 13C. High resolution mass
spectra were obtained using an Agilent G1969A spectrometer.
Electronic absorption spectra were obtained using a Perkin Elmer
LAMBDA 2S UV/Vis Spectrophotometer. Solid state absorption
spectra were obtained using a Perkin Elmer Lambda 900 UV/Vis/
NIR Spectrometer. The solution and solid state emission spectra
were measured on a Varian Cary Eclipse fluorescence spectrometer.
Solid crystalline film samples of compounds 1a–1d and 2a–2c
were fabricated by vacuum deposition of compounds on glass
slides, the temperature was monitored to avoid the thermal
decomposition of Schiff bases.21
This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2014
View Article Online
NJC
Synthesis and characterization
Schiff base derivatives 1a–1d and 2a–2c were prepared by using
two methodologies. Method A: 4-dimethylamino-trans-cinnam-
aldehyde and the corresponding aminoalcohol in equimolar
amounts were stirred for 1.5 h under reflux of methanol, except
for compound 1b which was refluxed in toluene–ethanol for 3 h.
The solvent and water formed during the reaction were removed
using a Dean-Stark trap to yield a solid, which was washed with
n-hexane–ethyl acetate mixtures (9 : 1). Method B: a methanolic
solution of 4-dimethylamino-trans-cinnamaldehyde and the
corresponding aminoalcohol containing acetic acid in catalytic
amounts were stirred for 30 min using an ultrasonic bath. Then
the iminic product was precipitated and separated by filtration
and finally washed with hexane. For compound 1a spectro-
scopic data were compared with the reported data.34c Complete
spectroscopic data are provided in the ESI.†
X-ray diffraction analysis, data collection and theoretical
calculations
Single crystals of compounds 1b, 1d and 2a suitable for X-ray
diffraction were obtained by slow evaporation from a saturated
chloroform or dichloromethane solution of the different Schiff
bases at room temperature. In the case of compound 1c the
obtained crystals were weak; however the structure was solved
with good reliability. The crystal data were recorded on an
Enraf Nonius Kappa-CCD (l MoKa = 0.71073 Å, graphite
monochromator, T = 293 K). Each crystal was mounted on
conventional MicroLoopst. All reflection data set were correc-
ted for Lorentz and polarization effects. The first structure
solution was obtained using the SIR2004 program and then
the SHELXL-97 programs were applied for refinement and
output data. All software manipulations were done using the
WinGX environment program set.22 Molecular perspectives
were drawn using the SHELXTL-XP23 drawing application and
Mercury Crystal Structure Visualization software.24 Some intra-
and intermolecular interactions were analyzed using OLEX225
and Platon26 software packages. All heavier atoms were found
using a difference Fourier map and refined anisotropically. The
hydrogen atoms were geometrically modeled except for those
involved in the hydrogen bonds which were found on the
difference Fourier map. The crystal features and data collection
are summarized in Table S1 (ESI†). The molecular structures of
1b, 1c and 2a are shown in Fig. 1.
Theoretical calculations
Molecular geometry and Frontier Molecular Orbitals (FMOs)
were obtained using the Density Functional Theory (DFT)
calculations performed in the Gaussian 03 code27 through
the hybrid functional of Becke28 with a gradient-correlation
functional of Lee, Yang and Parr29 B3LYP and a split-valence
polarized 6-31G(d) basis set to consider medium/large
sized molecules. Time Dependent-Density Functional Theory
(TD-DFT)30 with the Polarizable Continuum Model31 (PCM)
was used for oscillator strength calculation at the same level
of theory.
New J. Chem., 2014, 38, 730--738 | 731

NJC
Published on 25 November 2013. Downloaded by St. Petersburg State University on 07/02/2014 03:11:41.
Fig. 1 ORTEP diagram of compounds 1b, 1c and 2a, thermal ellipsoids are
drawn at 30% level for all atoms except H.
Nonlinear optical measurements
The second nonlinear response as a mb product for compounds 1a,
2a and 2b was experimentally determined by using an Electric Field
Induced Second-Harmonic (EFISH) technique.32 The EFISH experi-
mental setup is described as follows: a Nd:YAG laser emitting
picosecond pulses (1.064 mm) at a 10 Hz repetition rate was used
to pump a hydrogen cell (1 m long, 50 bar). The outcoming Stokes-
shifted radiation at 1.907 mm generated by the Raman effect was
used as the fundamental beam to carry out the EFISH measure-
ments. This fundamental beam was focused into a cell with quartz
window in a wedge configuration containing dichloromethane
solutions of Schiff bases at 5 and 10 mM. The centrosymmetry of
the solution was broken by dipolar orientation of the chromophores
applying a high voltage (5 kV) synchronized with the laser pulses.
The second-harmonic signal (at 953.5 nm) was selected through a
suitable interference filter, and detected by a photomultiplier tube.
The SHG efficiencies in the solid state were evaluated by the
Kurtz–Perry powder test.33 Samples were prepared by crushing
crystalline powder between two transparent glass substrates.
The efficiencies were quantified versus a reference sample of
powdered urea.
Results and discussion
Synthesis and characterization
Schiff bases 1a–1d and 2a–2c were prepared by reaction of
4-dimethylaminocinnamaldehyde with the corresponding amino-
alcohol, by using both conventional heating and ultrasonic stirring.
The formation of the imine derivatives was established in
solution by using 1H and 13C NMR experiments. The structure
of compounds 1b, 1c and 2a in the solid state was also corro-
borated by X-ray diffraction analysis (Fig. 1).
X-ray diffraction analysis of Schiff bases 1b, 1c and 2a
Compounds 1b and 1c crystallized in the orthorhombic
P212121 and Pca21 space groups containing four molecules
732 | New J. Chem., 2014, 38, 730--738 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2014
View Article Online
Paper
per unit cell, respectively. Compound 2a crystallized in the
monoclinic P21 space group containing two molecules per unit
cell. The molecular structures of compounds 1a–1d and 2a–2c
consist of an electronic p-system from the cinnamaldehyde
derived fragment connected to an aromatic ring or aliphatic
fragment, having a hydroxy group in different positions. The
bond distances from N1 to C7 (CQN) for compounds prepared
from aromatic amines 1b (1.289(3) Å) and 1c (1.288(4) Å) are
within the interval reported for other Schiff bases derived from
cinnamaldehyde (from 1.261(3) to 1.286(3) Å).34 For compound
2a, prepared from an aliphatic amine, the CQN (1.2774(18) Å)
distance values are in accordance with distances previously
reported.35
X-ray diffraction analysis of derivatives 1b, 1c and 2a showed
that the main p-backbone has a semi-planar conformation,
wherein the benzylalcohol ring (for 1b and 1c) or the aliphatic
chain (in 2a) is out of the molecular plane (plane A, Fig. S1,
ESI†). The A plane in compounds 1b, 1c and 2a is defined by the
dimethylamino-cinnamaldimine fragment and the B plane is
defined by the alcohol fragment. Analysis of the torsion angle for
the C7–N1–C8–C9 fragment shows that imine 1b (52.81(4)1)
has the largest value of the aromatic Schiff bases, this compound
has a CH2OH group in the ortho-position, which is responsible
for the large torsion angle value due to the steric effect. In the
case of 1c the torsion angle of the same fragment is 42.49(2).
For compound 2a the torsion angle of 98.5(2)1 is due to the lack
of electronic conjugation with the amine-alcohol fragment. Bond
distances and torsion angle values for 1a were taken from
ref. 34c and those of 1b, 1c and 2a are given in the ESI.†
The typical conformation of imine derivatives from cinnam-
aldehyde is non planar showing a deviation of 271 out of the
phenyl group plane,34 in contrast, Schiff bases 1a, 1b, 1c and 2a
showed shorter deviations of 12.41, 4.01, 4.31 and 7.61, respec-
tively, attributed to the presence of a strong donor group which
promotes the planar conformation increasing the quinoid
character through an intramolecular charge transfer process
from the NMe2 group to the imine nitrogen atom.36
It is to be noted that the crystal packing for 1b and 1c is
governed by hydrogen bond and C–H  p interactions (1c shows
4 contacts and 1b has 3); in 1a by a non classical hydrogen
bond34c (C–H  O) and compound 2a does not display any close
contact (Fig. 2, see Fig. S2, ESI† for supramolecular assembly).
Then, the crystal packing for 2a is purely governed by the
CQN  H–O hydrogen bonding interaction, which is an impor-
tant consideration for open packing.37 The O–H  N hydrogen
Fig. 2 Crystal packing diagrams of 1b, 1c and 2a along the a axis.
 View Article Online

Paper NJC

bond parameters in 1b, 1c and 2a indicate an O  N distance of
2.7737(2), 2.8466(4) and 2.7598(19) Å, respectively. Clearly,
compound 2a has the shortest O  N bond length probably due
to the flexibility of the aliphatic fragment. The intermolecular
interactions have been considered a fundamental factor for
photochromism in the solid state since the photophysical
properties are related to crystal packing.10 It is important to
mention that compounds 1a,34c 1b and 1c show structures with
Published on 25 November 2013. Downloaded by St. Petersburg State University on 07/02/2014 03:11:41.
excitation induces significant geometric changes in the excited
state of compound 2a. We attributed this behavior to the presence
of the relatively large phenylglycinol fragment with high confor-
mational and rotational freedom. On the other hand, 1a, 1b and
1d do not present photoluminescence properties.
Solid-state characterization of compounds 1a–1d and 2a–2c:
photochromic properties. The absorption and emission spectra in

close packing that prevent subtle changes in the molecule
through irradiation, as can be seen in the spacefill representation
(Fig. S1, ESI†).
In contrast, the phenylglycinol fragment in compound 2a
prevents close contact between molecules leading to an open-
structure packing15a that can present photochromism. More-
over, the phenylglycinol ring is clearly twisted out of plane with
respect to the same ring of the other molecule in the unit cell
(the centrosymmetric dimer) due to steric hindrance. For this
reason, the size and shape of this fragment are suitable to
create spaces for the photoinduced motion, a favorable condi-
tion in photochromism.
The presence of the intermolecular hydrogen bond in 2a
contributes to the crystal packing and promotes proton transfer;
at the same time, it contributes to give the necessary rigidity to
the molecule, to maintain the observed fluorescence.
Although compounds 1c and 2a exhibit similar supramolecular
arrangements (Fig. S2, ESI†), in the structure of 2a there are no
molecular layers parallel to the phenylglycinol plane and the
alcoholic fragment is not stacked along any crystallographic axis,
so that no p–p interactions are observed (p  p distances are 4.830 Å
in the direction of the c axis). For this reason, we propose that the
intermolecular proton transfer from O1 to N1B is through the
O1–H  N1B channel forming the O1  H–N1B mode.
the solid state were measured for compounds 1a–1d and 2a–2c.
The crystalline films were fabricated as described in the experi-
mental section. The photochromic properties in the solid state
were determined under continuous UV irradiation provided by a
Hg/Xe lamp (Hamamatsu, LC6 Lightningcure, 200 W) equipped
with a narrow band interference filter of 365 nm (Semrock Hg01
for lirr). The results indicate that the films of Schiff base 2a show
photochromic behavior (color change from yellow to red). The
absorption spectroscopy technique was employed to corroborate
the change in color; the spectra of the UV-irradiated film of 2a are
shown in Fig. 3a. Formation of a new red-shifted band was
observed after 5 seconds of irradiation, the intensity of this band
increased with the irradiation time (measured up to 80 seconds).
The new red-shifted band was attributed to the p - p* electronic
transition of the protonated imine conjugated p-system due to
intermolecular hydrogen transfer from the hydroxyl to the imino
nitrogen atom. Moreover, the interaction with the –N(Me)2 group
was discarded in a previous work where the ionochromic pro-
perties have been studied.39 Interestingly, the back reaction only
takes place thermally when the crystalline sample was heated to
B114 1C. In accordance with this, no photochemical reaction was
observed even when we irradiated at 410 nm.

Optical characterization of 1a–1d and 2a–2c in solution and in

the solid state
Table 1 summarizes the UV-Vis absorption and emission data
with the corresponding molar absorption coefficients for com-
pounds 1a–1d and 2a–2c in toluene and acetonitrile. In these
solvents we observed only one absorption maxima for each
compound. Analysis of Stokes shifts revealed that derivative 2a
has the largest value (6063 cm1), which implies the lowest
probability of having reabsorption of the fluorescence light,38
followed by compounds 2c, 2b and 1c with 5776, 5618 and
4946 cm1, respectively. This result indicates that electronic

Table 1 UV-Vis absorption and emission data for 1a–1d and 2a–2ca

lmax(abs) [nm] lmax(em) [nm] emax [M1 cm1]

Compound Toluene ACN Toluene ACN Toluene ACN
1a 408 404 — — 27 580 24 724
1b 393 384 — — 33 528 50 183
1c 382 382 430 471 17 216 47 002
1d 382 384 — — 53 748 59 897
2a 359 356 416 454 49 023 45 792
2b 358 356 415 445 45 183 46 634
Fig. 3 (a) UV-Vis absorption and (b) fluorescence emission spectra of 2a
2c 357 354 412 445 99 637 69 681
crystal powder under UV irradiation (365 nm) at room temperature. Inset:
a
Concentration 3.0  105 M. ACN: acetonitrile. absorption intensity difference under irradiation.

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2014 New J. Chem., 2014, 38, 730--738 | 733

NJC
Additionally, the solid state fluorescence spectrum of 2a
showed a main emission band at around 510 nm. The fluores-
cent properties of 2a film were investigated during the irradiation
experiment, the emission spectra showed gradual decrements of
intensity from 0 to 80 seconds, and it was practically quenched at
200 seconds, Fig. 3b. In this case, the fluorescence quenching was
attributed to the formation of the protonated imino nitrogen
through an intermolecular O–H  N hydrogen bond channel. This
Published on 25 November 2013. Downloaded by St. Petersburg State University on 07/02/2014 03:11:41.
is in agreement with the fact that some hydrogen donor molecules
become more acidic in the excited state.40
To investigate the effect of crystal packing on the photo-
chromic properties of Schiff base 2a, polymeric thin films were
prepared by using the guest (molecule)–host (polymer) approach.
The solid films were deposited on a glass substrate from a
chloroform solution of the inert matrix (polystyrene, 70%) and
imine (30%) by using the spin-coating method, the polystyrene
matrix inhibits the close contact of molecules in the film and in
this way the O–H  N intermolecular hydrogen bond was avoided.
The UV-irradiation experiments of the thin film produced a
reduction of the intensity in the absorption band of 2a, probably
due to photodegradation of the Schiff base.
Second-harmonic generation (SHG). SHG measurements
were performed on single crystals of 2a to confirm their
noncentrosymmetric structure and to evaluate their potential
use as a second-order NLO material. As expected, the enantio-
merically pure compound crystallized in a non centrosymmetric
space group, and generates second harmonics. The bm value
(170 esu) was measured by using the EFISH technique. Then,
the bulk SHG measured from the crystals was approximately
6 times larger than that of urea crystals.
Solvatochromism. In order to understand the effect of the
media on the photophysical properties of 2a, we carried out a
solvatochromic analysis. The experimental absorption and emis-
sion spectra of 2a in different solvents are shown in Fig. 4; the
position of the absorption band shows a non monotonic behavior
with respect to solvent polarity. However, in solvents like chloro-
form, DCM, methanol and phenyl-propanol, compound 2a showed
an additional absorption band at 477, 475, 469 and 479 nm,
respectively. The new red-shifted band of 2a can be attributed to
other solute–solvent interactions such as acidity since chloroform,
Fig. 4 UV-Vis absorption (a) and photoluminescence (b) spectra of 2a in different solvents.
734 | New J. Chem., 2014, 38, 730--738 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2014
View Article Online
Paper
dichloromethane (DCM) and methanol have a considerable acidity
with respect to the other solvents employed in this analysis.
The effect of solvent interactions on the absorption and
photoluminescence spectra of compound 2a was investigated
in terms of the Lippert–Mataga approximation. This descrip-
tion is based on the analysis of the linear relationship between
solvent polarity and experimental spectral shift obtained in a
series of solvents. In particular, the Lippert theory considers
that the absorption and emission spectral shifts are due to
specific solvent effects; hydrogen bonding and CT interactions
are some of these effects, however several specific interactions can
also give nonlinear Lippert plots, such as preferential solvation,
acid–base effects, hydrogen bonding (solvent–solute), etc.41 The
Lippert–Mataga equation relates Stokes shift and solvent polarity
according to eqn (1):

2
2 me  mg
Dn ¼ uA  uF ¼ ðDf Þ þC (1)
hc a3
where nA and nF are the wavenumbers (in cm1) of the absorp-
tion and emission, respectively, h is Planck’s constant, c is the
speed of light, a is the Onsager radius, and Dm = me  mg is the
dipole moment difference between the ground and excited
states. The solvent polarity Df is defined in terms of the dielectric
constant (e) and the refractive index (n) of the solvent (eqn (2)).
When Lippert–Mataga plots exhibit a linear behavior, the general
solvent effects are dominant in the spectral shifts.
 
e1 n2  1
Df ¼ f ðeÞ  f ðn2 Þ ¼  2 (2)
2e þ 1 2n þ 1
On the other hand, when they exhibit a non-linear behavior,
the specific solvent effects govern the spectral shifts which is
regarded as evidence of specific solute–solvent interactions
(Table 2).
It can be seen in Fig. 3a that the absorption band does not
display significant shifts due to variations in solvent polarity.
In contrast, the photoluminescence spectra evidence certain
red-shifting in the emission bands as the polarity increases
which suggests that the dipole moment is larger in the excited-
state than in the ground-state. In order to have experimental
evidence of the intramolecular charge transfer process taking
 View Article Online

Paper NJC

Table 2 Photophysical properties of compound 2a in different solventsa More recently, an empirical methodology to explain experi-
mental solvatochromic properties of chromophores from theore-
la na le ne
Solvent e n Df (nm) (cm1) (nm) (cm1) na  ne tical solvent characteristics was developed by Catalán.44 It is well
known that the relationship between solvent effects and spectral
Cyclohexane 2.02 1.4235 0 352 28 409 402 24 876 3533
Dioxane 2.22 1.4224 0.021 354 28 249 416 24 038 4211 shifts can be denoted by a multilinear equation.45 The new
Toluene 2.38 1.4961 0.013 359 27 855 416 24 038 3817 mathematical treatment of solvent effects introduced by Catalán
Diethyl ether 4.267 1.3526 0.165 350 28 571 413 24 213 4358 is based on four empirical and independent solvent scales.
Chloroform 4.81 1.4459 0.148 311 32 154 529 18 903 13 251
Published on 25 November 2013. Downloaded by St. Petersburg State University on 07/02/2014 03:11:41.

Ethyl acetate 6.081 1.3723 0.201 356 28 090 428 23 364 4726
y = y0 + aSASA + bSBSB + cSPSP + dSdPSdP (3)
THF 7.52 1.405 0.210 354 28 249 427 23 419 4830
DCM 8.93 1.4242 0.217 362 27 624 521 19 193 8431
Here SA, SB, SP and SdP are the solvent acidity, basicity,
Octanol 10.3 1.4295 0.225 363 27 548 429 23 310 4238
PhPrOH 11.97 1.5357 0.202 375 26 667 436 22 936 3731 polarizability and dipolarity properties, respectively. The coeffi-
n-Butanol 17.50 1.3988 0.264 361 27 700 444 22 522 5178 cients aSA, bSB, cSP and dSdP represent the contribution of each
i-PrOH 20.18 1.3776 0.277 361 27 701 440 22 727 4974
type of interactions. Then, a Catalán solvent analysis was
n-PrOH 20.8 1.385 0.275 361 27 701 444 22 523 5178
Acetone 21.01 1.3588 0.285 354 28 249 447 22 371 5878 carried out in order to understand the solvent parameters that
EtOH 25.3 1.3611 0.289 364 27 473 451 22 173 5300 affect the photophysical properties ( n abs, nem and D
n ) in com-
MeOH 33 1.3288 0.308 365 27 397 453 22 075 5322
pound 2a. The {SA, SB, SP, SdP} parameters for each solvent are
ACN 36.64 1.3442 0.305 356 28 090 454 22 026 6064
DMF 36.70 1.4305 0.274 358 27 933 451 22 172 5761 taken from ref. 44. The regression coefficients yo, aSA, bSB, cSP
DMSO 46.68 1.4793 0.263 357 28 011 455 21 965 6046 and dSdP, standard errors and the multilinear correlation
a
Dielectric constant, (e), refractive index, (n);46 orientation polarizability, coefficient, r, for 2a are presented in Table 3. In the case of
(D f ); absorption wavelength, (la); absorption wavenumber, ( n a); emission nabs, a good multilinear fit of 0.919 was obtained, due to the
wavelength, (le); emission wavenumber, ( n e). Solvent notation: THF (tetra- proton transfer emission promoted by chloroform and dichloro-
hydrofuran), DCM (dichloromethane), PhPrOH (3-phenyl-1-propanol),
i-PrOH (iso-propanol), n-PrOH (n-propanol), EtOH (ethanol), MeOH methane these two solvents were excluded just for the multi-
(methanol), ACN (acetonitrile), DMF (dimethylformamide), DMSO linear regression analysis. The analysis indicates that the major
(dimethyl sulfoxide). factors contributing to the solvatochromic changes in nabs are
the acidity and polarizability of the solvent, since the coefficient
place in 2a, the Dm values were calculated from the Lippert– values aSA and cSP are relatively large and have small standard
Mataga plots. The graph of Stokes shift as a function of solvent errors, in particular the analysis of data indicates that solvent
polarity for 2a shows three regions: the non-polar (0.0–0.15), acidity is the dominant effect. However, the SP parameter is in
the polar-aprotic (0.2–0.3) and the polar-protic (0.2–0.31). fact an influencing factor because the multilinear regression
Each region of the plot shows a linear behavior if they are without considering SP gives a lower r-value according to
considered separately (Fig. S3, ESI†). Thus from the slope in the eqn (3), namely, 0.874 for {SA, SB, SdP} variables, here the
polar region of the Lippert–Mataga plot a Dm of 15.1 D (slope = r-value is improved when the SP factor is considered (r = 0.913)
13 752  1975, R2 = 0.87) was estimated using an Onsager indicating that the solvent polarizability factor should not be
radius of 5.5 Å for 2a estimated by Density Functional Theory neglected. This is in agreement with the push–pull character of
(DFT).28 The Dm value calculated for 2a is comparable to the the molecule, observing a poor linear correlation of 0.78 between
values reported in the literature (3–20 D) for other solvato- the dielectric constant (e) and nem, because specific effects are
chromic fluorophores.42 also taking place, Fig. S3 (ESI†).
Additionally, the non-polar region of the Lippert–Mataga Furthermore, the relationship of nabs vs. the high frequency
plot exhibits a clear non-linear trend. This result is due to the polarizability function squared f (n2) = (n2  1)/(2n2 + 1) in 2a
fact that in the non-polar region, the solvation is less effective provides further evidence (Fig. S3, ESI†) of a non-linear trend
and there is no good reorientation of non-polar solvent dipoles (r = 0.064) indicating a large difference between ground-state
around the fluorophore. In the polar-protic region the esti- and excited-state dipole moments (Dm).47,48
mated Dm value was 16.2 D (slope = 15 895  2150, R2 = 0.90). In the case of nem and D n the largest values also were aSA,
The bi-linear behavior (overall non-linear) suggests that solvent cSP and dSdP accompanied by the smallest standard errors as in
polarity is not the only factor affecting the Stokes shifts, such the case of nabs analysis, indicating that the predominant factor
that specific solvent effects including hydrogen bonding and influencing the solvatochromic changes in nem and D n is
intramolecular charge transfer, preferential solvation and/or solvent acidity, although polarizability and dipolarity cannot
acid–base effects, are present.43 be neglected.

n (in cm1) and the multiple correlation coefficient (r) for regression analysis of
Table 3 Estimated coefficients y0, aSA, bSB, cSP and dSdP for nabs, nem, and D
compound 2a in 16 solvents according to the Catalán solvent parameters {SA, SB, SP, SdP} listed in Table S2

Observable y0 (cm1) aSA bSB cSP dSdP r

nabs 29 464  513 1728  277 39  218 1723  723 133  155 0.919
nem 25 892  613 1292  331 235  260 1438  864 2837  186 0.984
Dn 3571  679 435  367 195  289 285  958 2704  206 0.973

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2014 New J. Chem., 2014, 38, 730--738 | 735

NJC
In addition, the relationship between nem vs. f(n2) = (n2  1)/
(2n2 + 1) also shows a clear non-linear trend (r = 0.029)
corroborating the existence of a large Dm value.
Dilute acetic acid titration of compound 2a
Since Catalán analysis for 2a revealed that solvent acidity is the
most important parameter influencing the spectroscopic prop-
Published on 25 November 2013. Downloaded by St. Petersburg State University on 07/02/2014 03:11:41.
erties in solution, the sensitivity of this Schiff base to the acidity
of the media was evaluated by titration in acetonitrile solution
with an acetic acid : acetonitrile mixture (1 : 99, v/v). The absorp-
tion spectra of the titration (Fig. 5) show that as the acidity
increased the curve exhibited an isosbestic point. At the same
time, a red-shifted band at 477 nm is formed and the intensity
of the absorption band at 356 nm decreases. This new band is
in agreement with that observed in chloroform, DCM, MeOH
and PhPrOH and also with the band detected in the thin film
experiment after irradiation. Furthermore, the titration process
of compound 2a was investigated by using fluorescence
spectroscopy. The photoluminescence spectrum (Fig. 5b) shows
that an increase in acidity promotes the complete fluorescence
quenching of 2a in solution. A plausible explanation of these
spectral results is the protonation of the imine nitrogen atom.
The protonation of the N(Me)2 group at low acid concentration
is discarded due to lower basicity and the quinoid character of
this fragment.49
Effect of –N(Me)2 in compound 2a
To confirm the existence of the protonated imine nitrogen and
the effect of the N(Me)2 group, we synthesized compound 3
(analogue of compound 2a without the N(Me)2 group).50 The
results show that 3 does not exhibit solvatochromic behaviour
when the spectra were taken in dioxane (284 nm) and ethanol
Fig. 5 Acetic acid titration of compound 2a. (a) Absorption spectra
showing an isosbestic point and (b) emission spectra showing fluores-
cence quenching.
736 | New J. Chem., 2014, 38, 730--738 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2014
View Article Online
Paper
(285 nm); however, in chloroform the protonated imine shows a
new red shifted band at 341 nm similar to the one observed in
2a (Fig. S4a, ESI†). Also, we performed the acetic acid titration
experiment for 3 in ethanol by adding the same acetic acid
solution observing again an isosbestic point due to the proto-
nated and non-protonated species, (Fig. S4b, ESI†). This result
supports the idea that the red-shifted band for 2a is mainly due
to the protonated imine species.
Theoretical calculations
The optimized structures and FMOs for compound 2a obtained
by theoretical analysis are illustrated in Fig. 6. Comparison of
these results with structural experimental data indicates that
the estimated conformation is similar to the one obtained by
X-ray diffraction analysis. Fig. 6 shows the electronic absorption
spectra and the calculated oscillator strength for 2a, Table 4
presents the major electronic transition contribution to the
theoretical electronic absorption spectra for this compound in
the gas phase, cyclohexane, acetonitrile and methanol obtained
by TD-DFT. The main absorption band can be ascribed to a
n - p* electronic transition with a main contribution of
HOMO–LUMO where the HOMO level is predominantly located
on the dimethylamino-cinnamaldimine moiety, while the LUMO
level is located on the cinnamaldimine moiety, giving an
intramolecular charge transfer (ICT) character to the molecule.
Further evidence of the ICT comes from the observed solvato-
chromic behavior in the absorption spectra of 2a, exhibiting a
bathochromic shift when solvent polarity is increased, accom-
panied by a more pronounced bathochromic shift in the
emission spectra. Taking into account the observed hydrogen
bonding interaction in the crystalline arrangement and titra-
tion experiments, we also computed the imino protonated
species (CQN+–H) observing a red shift of about 67 nm with
Fig. 6 Electronic absorption spectra and the calculated oscillator strength
of 2a in different solvents.

Paper
Table 4 Theoretically simulated electronic absorption spectra of 2a in
different media and HOMO–LUMO electronic transition contribution
Theoretical Oscillator Contribution
wavelength (nm) Medium strength (%)
339 Gas phase 1.1805 40
355 Cyclohexane 1.3053 41
361 Methanol 1.2811 41
361 Acetonitrile 1.2869 41
Published on 25 November 2013. Downloaded by St. Petersburg State University on 07/02/2014 03:11:41.
almost no change in the oscillator strength value, so we propose
that the photochromic behavior could be attributed to the forma-
tion of a quinoid character species that permits the p-conjugation
to fully spread through the chromophoric system.
We further investigated the electronic transitions giving rise
to the observed absorption band in the framework of TD-DFT
at the B3LYP/6-31G(d) level of theory by using the so-called
polarizable continuum model (PCM). The oscillator strength
values were reproduced in good agreement with the observed
experimental absorption bands (Table 4) where according to
TD-DFT/PCM the n - p* electronic transition is red-shifted.
Finally, the IR spectra of the protonated and non-protonated
species were calculated on the basis of vibrational frequencies
at the DFT (B3LYP/6-31G(d)) level of theory. The spectra show
two new bands at 3360 and 1660 cm1 which correspond to the
experimental change observed upon irradiation (l = 365 nm),
Fig. S4 (ESI†). These bands have been assigned to the formation
of the protonated imine (H–NQC–) fragment.51
Conclusions
In summary we report the synthesis of seven Schiff bases and the
photochromic behavior assisted by an OH  N intermolecular
hydrogen bond. Only Schiff base 2a derived from phenylglycinol
presented photochromism in the solid state. We propose that the
intermolecular proton transfer from the O1 atom to N1 takes
place through the O1–H  N1 channel forming the O1  H–N1
mode and is responsible for the change of color from yellow to
deep red in the crystalline state and thin films. Furthermore,
solid state fluorescence emission decreased with irradiation time
due to the subsequent intermolecular proton transfer. The
solvatochromic analysis revealed a strong influence of solvents
in 2a evidencing specific interactions with the medium. The
Lippert plot shows a non-linear behavior attributed to hydrogen
bonding interaction and intramolecular charge transfer. Interest-
ingly, Catalán analysis indicates that the major factor influencing
the solvatochromic changes for nabs, nem and D n is solvent
acidity. The influence of acidity on the absorption spectra con-
firms the formation of the protonated imine fragment (CQN+–H)
as evidenced by the formation of a red-shifted band, which is very
similar to the one formed in the solvatochromic analysis and also
in the solid state absorption spectra induced by UV-irradiation.
The solvatochromic results are also consistent with theoretical
calculations, since FMOs show an intramolecular charge transfer
(ICT) character in the molecule and, the oscillator strength values
well reproduced the observed experimental absorption spectra.
This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2014
View Article Online
NJC
Acknowledgements
The authors thank CONACyT (Projects 152820 and 183147) and
PAPIIT IN 214513 for financial support. Arturo Jiménez-Sánchez
thanks the ANUIES ECOS-NORD project and CONACyT for
the PhD fellowship; also the computer cluster Xiuhcoatl from
CINVESTAV-IPN.
Notes and references
1 (a) P. A. Vigato, S. Tamburini and L. Bertolo, Coord. Chem.
Rev., 2007, 251, 1311; (b) A. D. Garnovskii, A. L. Nivorozhkin
and V. I. Minkin, Coord. Chem. Rev., 1993, 126, 1.
2 (a) F. Faridbod, M. R. Ganjali, R. Dinarvand, P. Norouzi and
S. Riahi, Sensors, 2008, 8, 1645; (b) D. A. Safin, M. G.
Babashkina and Y. Garcia, Dalton Trans., 2013, 42, 1969.
3 N. Kaur and S. Kumar, Dalton Trans., 2012, 41, 5217.
4 (a) S. Vijayalakshmi and S. Kalyanaraman, Opt. Mater., 2013,
35, 440; (b) J. H. Jia, X. M. Tao, Y. J. Li, W. J. Sheng, L. Han,
J. R. Gao and Y. F. Zheng, Chem. Phys. Lett., 2011, 514, 114.
5 G. Grivani, V. Tahmasebi, A. D. Khalaji, K. Fejfarova and
M. Dusek, Polyhedron, 2013, 51, 54.
6 K. Brychcy, K. Drager, K. J. Jens, M. Tilset and U. Behrens,
Chem. Ber., 1994, 127, 465.
7 (a) L. Chen, J. Wei, N. Tang and F. Cheng, Catal. Lett., 2012,
142, 486; (b) L. Chen, F. Cheng, L. Jia, L. Wang, J. Wei,
J. Zhang, L. Yao, N. Tang and J. Wu, Appl. Catal., 2012,
415, 40.
8 M. Tumer, H. Koksal and S. Serin, Transition Met. Chem.,
1999, 24, 13.
9 D. Higelin and H. Sixl, Chem. Phys., 1983, 77, 391.
10 E. Hadjoudis, Photochromism, molecules and systems.
Studies in organic chemistry, Photochromism. Molecules
and systems, ed. H. Durr and H. Bouas-Laurent, Elsevier,
Amsterdam, 1990, ch. 17, vol. 40.
11 (a) A. Perrier, F. Maurel and D. Jacquemin, Acc. Chem. Res.,
2012, 45, 1173; (b) M. Irie, Photochem. Photobiol. Sci., 2010,
9, 1535.
12 (a) W. R. Browne, M. M. Pollard, B. Lange, A. Meetsma and
B. Feringa, J. Am. Chem. Soc., 2006, 128, 12412; (b) M. Sliwa,
S. Létard, I. Malfant, M. Nierlich, P. G. Lacroix, T. Asahi,
H. Masuhara, P. Yu and K. Nakatani, Chem. Mater., 2005,
17, 4727.
13 (a) S. Prashanthi, P. H. Kumar, D. Siva, S. R. Lanke, V. J. Rao,
S. Basak and P. R. Bangal, J. Phys. Chem. C, 2011, 115, 20682;
(b) R. Pardo, M. Zayat and D. Levy, Chem. Soc. Rev., 2011,
40, 672.
14 (a) E. Hadjoudis, A. Rontoyianni, K. Ambroziak,
T. Dziembowskac and I. M. Mavridis, J. Photochem. Photobiol.,
A, 2004, 162, 521; (b) E. Hadjoudis, S. Chatziefthimiou and
I. Mavridis, Curr. Org. Chem., 2009, 13, 269; (c) K. Amimoto
and T. Kawato, J. Photochem. Photobiol., C, 2005, 6, 207;
(d) M. Ziólek, F. Katarzyna and A. Maciejewski, Chem. Phys.
Lett., 2008, 464, 181.
15 (a) M. I. J. Stich, L. H. Fischer and O. S. Wolfbeis, Chem. Soc.
Rev., 2010, 39, 3102; (b) X. F. Yang, Y. X. Guo and
New J. Chem., 2014, 38, 730--738 | 737

NJC
R. M. Strongin, Angew. Chem., Int. Ed., 2011, 47, 10690;
(c) H. F. Higginbotham, R. P. Cox, S. Sandanayake, B. A.
Graystone, S. J. Langford and T. D. M. Bell, Chem. Commun.,
2013, 49, 5061.
16 J. J. Lavigne and E. V. Anslyn, Angew. Chem., Int. Ed., 2001,
40, 3118.
17 (a) I. Bolz, C. May and S. Spange, New J. Chem., 2007,
31, 1568; (b) S. Spange, D. Kunzmann, R. Sens, A. Seifert,
Published on 25 November 2013. Downloaded by St. Petersburg State University on 07/02/2014 03:11:41.
I. Roth and W. Thiel, Chem.–Eur. J., 2003, 9, 4161.
18 M. Rodrı́guez, R. Santillan, Y. López, N. Farfán, V. Barba,
K. Nakatani, E. V. Garcı́a Baéz and I. I. Padilla-Martı́nez,
Supramol. Chem., 2007, 19, 641.
19 O. Domı́nguez, B. Rodrı́guez-Molina, M. Rodrı́guez, A. Ariza,
N. Farfán and R. Santillan, New J. Chem., 2011, 35, 156.
20 M. Rodrı́guez, J. L. Maldonado, G. Ramos-Ortı́z, J. F. Lamere,
P. G. Lacroix, N. Farfán, Ma. E. Ochoa, R. Santillan, M. A.
Meneses-Nava, O. Barbosa-Garcı́a and K. Nakatani, New J. Chem.,
2009, 33, 1693.
21 A. Spangenberg, A. Brosseau, R. Metivier, M. Sliwa,
K. Nakatani, T. Asahi and T. Uwada, J. Phys. Org. Chem.,
2007, 20, 985.
22 L. J. Farrugia, J. Appl. Crystallogr., 1999, 32, 837.
23 G. M. Sheldrick, SHEXL-97. Program for crystal structure
solution, University of Göttingen Germany, 1997.
24 C. F. Macrae, I. J. Bruno, J. A. Chisholm, P. R. Edgington,
P. McCabe, E. Pidcock, L. Rodriguez-Monge, R. Taylor, J. van
de Streek and P. A. Wood, J. Appl. Crystallogr., 2008, 41, 466.
25 O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, A. K. Judith,
A. K. Howard and H. Puschmann, J. Appl. Crystallogr., 2009,
42, 339.
26 A. L. Spek, Acta Crystallogr., Sect. A: Found. Crystallogr., 1990,
46, c34.
27 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb and J. R. Cheeseman, et al., Gaussian 03, Revision
C.02, Gaussian, Inc., Wallingford CT, 2004.
28 (a) A. D. Becke, J. Chem. Phys., 1993, 98, 5648; (b) A. D. Becke,
J. Chem. Phys., 1997, 107, 8554.
29 C. Lee, W. Yang and C. R. Parr, Phys. Rev. B: Condens. Matter
Mater. Phys., 1988, 37, 785.
30 (a) D. Jacquemin, E. Brémond, I. Ciofini and C. Adamo,
J. Phys. Chem. Lett., 2012, 3, 468; (b) D. Jacquemin,
V. Wathelet, E. A. Perpète and C. Adamo, J. Chem. Theory
Comput., 2009, 5, 2420.
31 (a) C. Amovilli, V. Barone, R. Cammi, E. Cancès, M. Cossi,
B. Mennucci, C. S. Pomelli and J. Tomasi, Adv. Quantum
Chem., 1998, 32, 227; (b) J. Tomasi, B. Mennucci and
R. Cammi, Chem. Rev., 2005, 105, 2999.
32 B. F. Levine and C. G. Betha, J. Chem. Phys., 1975, 63, 2666.
33 (a) S. K. Kurtz and T. T. Perry, J. Appl. Phys., 1968, 39, 3798;
(b) J. P. Dougherty and S. K. Kurtz, J. Appl. Crystallogr.,
1976, 9, 145.
738 | New J. Chem., 2014, 38, 730--738 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2014
View Article Online
Paper
34 (a) Y. Li, X. Yang, S. Zhang and X. Li, Acta Crystallogr., Sect.
E: Struct. Rep. Online, 2005, 61, o3337; (b) V. Nesterov,
A. Suina, Y. Antipin, T. Timofeeva, S. Barlowc and
S. Marder, Acta Crystallogr., Sect. C: Cryst. Struct. Commun.,
2003, 59, o625; (c) M. Rodrı́guez, R. Castro-Beltrán, G. Ramos-
Ortı́z, J. L. Maldonado, N. Farfán, O. Domı́nguez, J. Rodrı́guez,
R. Santillan, M. A. Meneses-Nava, O. Barbosa-Garcı́a and
J. Peon, Synth. Met., 2009, 159, 1281.
35 L. Ying, H. Xiao-Lian and Y. Xiao-Yan, Acta Crystallogr., Sect.
E: Struct. Rep. Online, 2007, E63, o4546.
36 The quinoid character is also present in compounds 1b, 1c
and 2a: For 1a C2–C3 (1.373), C2A–C3A (1.371); C2–C1
(1.404), C1–C2A (1.403), C3A–C4 (1.395) and C4–C3 (1.394) Å.
For 1b C2–C3 (1.370), C2A–C3A (1.374); C2–C1 (1.395), C1–C2A
(1.399), C3A–C4 (1.395), C4–C3 (1.396) Å. For 1c C2–C3 (1.367),
C2A–C3A (1.367), C2–C1 (1.397), C1–C2A (1.391), C3A–C4
(1.382), C4–C3 (1.394) Å.
37 A. I. Kitaigorodskii, Organic Chemical Crystallography,
Consultants bureau, New York, 1961, Section 2.
38 H. Langhals and A. Hofer, J. Org. Chem., 2012, 77, 9585.
39 A. Jiménez-Sánchez, N. Farfán and R. Santillan, Tetrahedron
Lett., 2013, 54, 5279.
40 M. Klessinger and J. Michl, Excited States and Photochemistry
of Organic Molecules, VCH Publishers, 1995, ch. 1.
41 (a) E. Lippert, IUPAC Symposium on Hydrogen Bonding, Ljubljana,
1957; (b) W. E. Acree Jr., D. C. Wilkins, S. A. Tucker, J. M. Griffin
and J. R. Powell, J. Phys. Chem., 1994, 98, 2537; (c) R. Królicki and
W. Jarzȩba, J. Phys. Chem. A, 2002, 106, 1708.
42 (a) M. Utinans and O. Neilands, Adv. Mater. Opt. Electron.,
1999, 9, 19; (b) Y. Gong, X. Guo, S. Wang, H. Su, A. Xia, Q. He
and F. Bai, J. Phys. Chem. A, 2007, 111, 5806.
43 S. Y. Fung, J. Duhamel and P. Chen, J. Phys. Chem. A, 2006,
110, 11446.
44 J. Catalán, J. Phys. Chem. B, 2009, 113, 5951.
45 M. J. Kamlet, J. L. M. Abboud, M. H. Abraham and
R. W. Taft, J. Org. Chem., 1983, 48, 2877.
46 D. R. Lide, CRC Handbook of Chemistry and Physics, ed.
D. R. Lide, CRC Press, 2002.
47 D. Pevenage, D. Corens, W. Dehaen, M. Auweraer and
F. C. De Schryver, Bull. Soc. Chim. Belg., 1997, 106, 565.
48 N. Boens, V. Leen, W. Dehaen, L. Wang, K. Robeyns, W. Qin,
X. Tang, D. Beljonne, C. Tonnelé, J. M. Paredes, M. J.
Ruedas-Rama, A. Orte, L. Crovetto, E. M. Talavera and
J. M. Alvarez-Pez, J. Phys. Chem. A, 2012, 116, 9621.
49 I. B. Dzvinchuk, Chem. Heterocycl. Compd., 2009, 45, 85.
50 J. Alladoum, S. Roland, E. Vrancken, C. Kadoury-Puchot and
P. Mangeney, Synlett, 2006, 1855.
51 (a) A. Filarowskia, T. Głowiaka and A. Koll, J. Mol. Struct.,
1999, 484, 75; (b) Y. Ito, K. Amimoto and T. Kawato, Dyes
Pigm., 2011, 89, 319; (c) P. Gilli, V. Bertolasi, V. Ferretti and
G. Gilli, J. Am. Chem. Soc., 2000, 122, 10405.