Novel thiophene-containing push-pull chromophores that include carbazole and triphenylamine moieties: study of optical and electrochemical properties

Article abstract of DOI:10.1007/s10593-016-1899-2

[Figure not available: see fulltext.] Novel carbazole- and triphenylamine-containing alkylidene malononitriles that include thiophene and bithienyl fragments as π-spacers were synthesized. Quantum-chemical calculations of the frontier molecular orbital energies were performed using the B3LYP/6-31G(d) method with regard to solvent. Electronic absorption spectra and fluorescence spectra were recorded for all the obtained compounds; their electrochemical properties were also studied. The experimental energy values of HOMO and LUMO levels were derived from resulting data. Thin films were obtained by the spin coating technique, and their surface morphology was studied using a NTEGRA Prima scanning tunneling microscope.

Full text of DOI:10.1007/s10593-016-1899-2

DOI 10.1007/s10593-016-1899-2
Chemistry of Heterocyclic Compounds 2016, 52(6), 379–387
Novel thiophene-containing push-pull chromophores
that include carbazole and triphenylamine moieties:
study of optical and electrochemical properties
1
1
2
2
Artur N. Bakiev , Darya G. Selivanova , Igor V. Lunegov , Aleksandr N. Vasyanin ,
1,2
1
1
2,3
Olga A. Maiorova , Aleksei A. Gorbunov , Elena V. Shklyaeva , Georgii G. Abashev *
1
Institute of Technical Chemistry, Ural Branch of the Russian Academy of Sciences,
3
Akademika Koroleva St., Perm 614013, Russia; e-mail: gabashev@psu.ru
2
3
Perm State National Research University,
5 Bukireva St., Perm 614990, Russia; e-mail: gabashev@psu.ru
Natural Science Institute, Perm State National Research University,
Genkel St., Perm 614990, Russia; e-mail: gabashev@psu.ru
1
4
Translated from Khimiya Geterotsiklicheskikh Soedinenii,
016, 52(6), 379–387
Submitted April 20, 2016
Accepted June 7, 2016
2
Novel carbazole- and triphenylamine-containing alkylidene malononitriles that include thiophene and bithienyl fragments as π-spacers
were synthesized. Quantum-chemical calculations of the frontier molecular orbital energies were performed using the B3LYP/6-31G(d)
method with regard to solvent. Electronic absorption spectra and fluorescence spectra were recorded for all the obtained compounds;
their electrochemical properties were also studied. The experimental energy values of HOMO and LUMO levels were derived from
resulting data. Thin films were obtained by the spin coating technique, and their surface morphology was studied using a NTEGRA
Prima scanning tunneling microscope.
Keywords: alkylidene malononitrile, carbazole, thiophene, triphenylamine, B3LYP/6-31G(d) method, chromophore, electrochemical
properties, optical properties.
Organic photovoltaic cells are attracting increased
attention as an alternative to traditional silicon solar cells,1
due to the possibility of using low-cost production
techniques to create a large area of multilayer structures on
distribution.11,12 These factors reduce the overall efficiency
,2
13
and stability of the devices.
Small-molecule solar cells are now becoming an alter-
native to polymer-based solar cells. On the one hand, they
exhibit properties inherent to polymers such as flexibility,
processability, the ability to form products from solutions.
On the other hand, these small molecules have a constant
molecular weight and their structure is strictly defined by
3–5
flexible substrates. There are two basic configurations of
organic photovoltaic cells: the planar-type battery in which
the photoactive components are applied in separate layers,
and the bulk-heterojunction battery in which there is only
one photoactive layer in the form of a mixture of the donor
the fact that these compounds can be purified to a high
6
14-18
and acceptor. It is known that the highest efficiency for
degree.
To achieve high efficiency for bulk-
solar cells with bulk-heterojunction has been achieved in
heterojunction photovoltaic cells, it is crucial to develop
new types of π-conjugated small molecules with a narrow
band gap, which is important for the efficient absorption of
sunlight, and with a high charge carrier mobility to transport
photogenerated charges to the electrodes.12 At present, much
attention is paid to the synthesis and study of organic
molecules of D-π-A structure, which is due to the possibility
7-10
the narrow band gap polymers.
Despite the significant
progress reached in the field of optimization of the bulk-
heterojunction solar cell characteristics, the use of poly-
meric materials in this area is limited due to the difficulties
of purification, complexity of controlling the ordering of
the structure, as well as a wide molecular weight
0
009-3122/16/52(6)-0379©2016 Springer Science+Business Media New York
379

Chemistry of Heterocyclic Compounds 2016, 52(6), 379–387
Scheme 1
to tune the optical and electronic properties of these
systems by varying the electron-donating and electron-
accepting moieties contained within their structure and by
introducing π-linkers of different nature, which, in turn,
allows to expand the range of absorption due to
intramolecular charge transfer from the donor to the
and more thiophene rings, such a shift disappears.24 There
are various methods for extension of the conjugated chain
by introducing various aryl and hetaryl fragments into the
structure of compounds mainly via metal-catalyzed
2
5-28
reactions,
competing with photocatalyzed CH hetero-
arylation reactions.2
9,30
We selected two synthetic
1
8-20
acceptor moiety.
It has been repeatedly shown that the
approaches for the introduction of thiophene and bithienyl
fragments into the conjugated chain. In the first case, the
Suzuki coupling of (9H-carbazol-9-yl)phenylboronic acid
presence of such fragments as carbazole, triphenylamine,
and thiophene within the semiconductor structure helps to
reduce the width of the band gap, resulting in the
improvement of transporting and photovoltaic properties
22
(2), synthesized by the previously described method, with
brominated thiophenecarbaldehydes 3, 4 in the presence of
1
5,21,22
due to efficient intramolecular charge transfer.
Pd(PPh
3
)
4
and Na
2
CO as the base (Scheme 1) was used.
3
This work presents the synthesis of novel D-π-A
structures containing electron-donating carbazole and
triphenylamine fragments, as well as the results of the
study of their properties. Dicyanovinylene moiety, capable
of increasing the electron affinity of the molecule of the
compound as a whole and reducing the band gap of the
conjugated system, was used as an acceptor (A). Thiophene
and bithienyl were selected as π-spacers for these
molecules in order to reduce the width of the band gap,
contributing to a stronger light absorption and expansion of
As a result, aldehydes 5, 6 were obtained.
The second method, based on the Vilsmeier–Haack–
Arnold acylation, presents a two-stage process, as a result
of which an additional acetyl thiophene fragment is formed
(Scheme 2). Initially, chloropropenals 8, 10 were syn-
thesized by interaction of phosphorus oxychloride, DMF,
and the corresponding methyl ketones 7 and 9, whose
further reaction with sodium sulfide in DMF and subsequent
treatment of the intermediate products with chloroacetone
resulted in the formation of 3-acetonyl-3-arylthiopropenals.
The cyclization of the latter by the action of a base
2
3
the absorption spectrum. This was confirmed by the
experimental data obtained by Japanese researchers,
according to which the introduction of an additional
thiophene ring in the structure of the molecule leads to a
bathochromic shift of 20 nm of the maximum absorption
band. However, on increasing the conjugated chain to four
(K
2
CO ) afforded 5-acetyl-5-arylthiophenes 9, 11. The
3
starting 1-(4-diphenylaminophenyl)ethanone (7), chloro-
propenal 8, and {5-[4-(N,N-diphenylamino)phenyl]thio-
31
phen-2-yl}ethanone (9) were obtained previously; the
methods of their synthesis was used in the present work.
Scheme 2
1
. POCl3, DMF
0°C, 3 h
1. Na2S, DMF
60°C, 3 h
O
Cl
6
N
N
O
H
N
2. NaOAc, H2O
pH 4
2. ClCH2COMe
60°C, 2 h
S
O
Me
Me
3
. K CO , H O
2 3 2
7
8
9
10 min
1
. POCl3, DMF
0°C, 3 h
1. Na2S, DMF
60°C, 3 h
6
N
N
2. NaOAc, H2O
pH 4
S
Cl
2. ClCH2COMe
60°C, 2 h
S
S
Me
O
3
. K2CO3, H2O
O
10
11
60°C, 10 min
H
3
80

Chemistry of Heterocyclic Compounds 2016, 52(6), 379–387
Scheme 3
Subsequent reaction of aldehydes 5, 6, 9 or ketones 11
Figure 1 shows the geometry of the HOMO and LUMO.
The electron density of the HOMO orbitals of all
compounds is located on the donor groups containing
carbazole, triphenylamine, and thiophene fragments. It has
been found that the largest electron density is concentrated
on the nitrogen atom. For compounds 12, 14, the electron
density in the LUMO orbitals is located mainly on the
acceptor moiety, whereas for compounds 13, 15, it is
located on the acceptor moiety and in part on the thiophene
linker.
with malononitrile in benzene in the presence of catalytic
amounts of ammonium acetate and acetic acid resulted in
the corresponding 2-(arylmethylidene)malononitriles 12,
1
3 and 2-(1-arylethylidene)malononitriles 14, 15 (Scheme 3).
Conjugated systems 12–15 were synthesized with an
aim to determine their potential as materials for bulk-hetero-
junction organic solar cells. To do this, the quantum-
chemical calculations of molecular orbital energies using the
B3LYP/6-31G(d) method taking into account the effect of
the solvent (chloroform, within the DPCM model) was initial-
To compare the data obtained by calculations with
experimental data, we investigated the optical and
electrochemical properties of the synthesized compounds
12–15. Absorption spectra and fluorescence spectra were
3
2,33
ly performed using the Firefly software
on a GPU Tesla
supercomputer. The geometry of the molecules was
preliminary optimized by the same method.
Calculations has shown that compounds 14, 15 with
triphenylamine moiety are characterized by large values for
the energies of the highest occupied (HOMO) and lowest
unoccupied (LUMO) molecular orbitals, compared with the
corresponding values found for carbazole compounds 12
and 13. Introducing of a second thiophene ring to the
structure of compounds 12, 14 increases electron-donating
properties of the systems that results in increasing of the
HOMO level, whereas the LUMO energy level changes
insignificantly. These parameters are important for the
calculation of the efficiency of the solar battery.34 It is
known that the energy gap between the LUMO level of an
electron-donating component of the solar cell (compound
with D-π-A structure) and the LUMO level of soluble
derivatives of fullerene (PCBM [60] or PCBM [70]), often
used as an electron-accepting component, should be 0.3 eV.
With a larger value, significant losses in the open-circuit
voltage (Voc) and light conversion efficiency (η) occur. To
achieve the maximum open circuit voltage, it is also
important to adjust the HOMO level energy of the donor
recorded for solutions of the compounds in chloroform.
opt
The HOMO–LUMO gap (E
g
) was calculated on the base
abs
of the absorption spectrum edge value (λonset ) by the
formula:
opt
E
g
= 1241/λonset,
where λonset – wavelength of the absorption spectrum
edge.37
Stokes shifts were calculated as the difference of the
wavelengths of the absorption and fluorescence maxima
(Table 1). This value indicates the amount of energy that is
consumed by a molecule in nonradiative processes, which is
important to determine the material of an organic electronic
device.
Figure 2 shows the absorption and emission spectra of
abs
compounds 12–15. There are four peaks (λmax ) in the
region of 280–550 nm in the UV absorption spectra of
compounds 12 and 13. Absorption maxima at 294, 327,
341 nm (compound 12) and at 295, 329, 342 nm
(compound 13) can be attributed to π–π* electronic transi-
tions. The long-wavelength absorption maxima at 433 nm
(compound 12) and 450 nm (compound 13) arise as a
3
5,36
material to a value of about –5.5 eV.
Figure 1. The energies of HOMO and LUMO levels of compounds 12–15 and their visualization after
optimization in the FireFly program using the B3LYP/6-31G(d) method.
3
81

Chemistry of Heterocyclic Compounds 2016, 52(6), 379–387
Table 1. Spectral characteristics of compounds 12–15
values were found for compounds 14 and 15, due to the
maxabs*,
onsetabs,
maxem**, Stokes
opt,
fact that structures containing triphenylamine moiety tend
to form a twisted conformation when excited, whereby part
of the energy is spent on geometric relaxation.39
Com-
pound
λ
λ
λ
E
g
eV
nm
nm
nm
545
599
611
656
shift , nm
1
1
1
1
2
3
4
5
294, 327, 341, 433
295, 329, 342, 450
307, 465
510
549
569
604
112
2.43
2.25
2.17
2.05
The electrochemical properties of the synthesized
compounds 12–15 were investigated by cyclic voltammetry
149
146
(
CV) using a MeCN–CH
2
Cl , 9:1 (v/v), mixture (Figs. 4, 5
2
303, 357, 477
179
and Table 2) as the medium. Based on the experimental
results, the energy of the frontier orbitals (HOMO, LUMO)
abs
max
– values of absorption maximum wavelength.
em
*
*
λ
* λmax – values of emission maximum wavelength.
was calculated. To evaluate the energy levels of the HOMO
and LUMO, the potentials for onset of oxidation (Eox
were determined.
onset
)
consequence of the existence of intramolecular charge
transfer (ICT) from a donor to the dicyanovinylene
acceptor moiety.1 Furthermore, the introduction of
additional thiophene fragments in the structure of
compound 13 led to a bathochromic shift of 17 nm of the
long-wavelength absorption maximum. The absorption
spectra of compounds 14 and 15 exhibit two (compound
Formulas (1) and (2) were used for the calculations:
5
E
HOMO = –(Eoxonset vs Ag/AgCl – EFc vs AgCl + 4.8) eV
(1),
where EFc vs AgCl = +0.41;40
op
(2).41
E
LUMO = EHOMO + E
g
eV
1
6
4) and three (compound 15) absorption maxima in 285–
70 nm range. Shortwave absorption peaks in the spectra of
Due to presence in the structure of compounds 12 and
13 of an unsubstituted carbazole moiety, these compounds
are able to undergo electrochemical oligomerization on the
surface of the working electrode.22 Redox processes in
compounds 12 and 13 occur in the range of 0.6 to 1.6 V
and from 0.8 to 1.7 V, respectively. The presence of two
reversible oxidation peaks indicates the initial formation of
a carbazole radical cation, which is converted to the
compounds 14 (307 nm) and 15 (303, 357 nm) are related
to the π–π* transition; long-wavelength absorption maxima
at 465 nm (compound 14) and 477 nm (compound 15)
3
8
result from intramolecular charge transfer.
Anomalously high values of the Stokes shift were
observed for all of the obtained compounds. The highest
Figure 2. а) Absorption spectra of compounds 12 (solid line) and 13 (dotted line); b) absorption
–
5
3
spectra of compounds 14 (solid line) and 15 (dotted line) (solvent CHCl , с 10 mol/l).
Figure 3. а) Emission spectra of compounds 12 (solid line) and 13 (dotted line); b) emission
–
5
3
spectra of compounds 14 (solid line) and 15 (dotted line) (solvent CHCl , с 10 mol/l).
3
82

Chemistry of Heterocyclic Compounds 2016, 52(6), 379–387
Figure 4. Cyclic voltammetry curves of compounds a) 12 and b) 13 (carbon pyroceramics
+
–
–1
working electrode, Et
4
N ClO
4
, Vscan 50 mV·s , MeCN–CH
2
Cl
2
, 9:1, 10 cycles).
Figure 5. Cyclic voltammetry curves of compounds a) 14 and b) 15 (carbon pyroceramics
+
–
–1
working electrode, Et
4
N ClO
4
, Vscan 50 mV·s , MeCN–CH
2
Cl
2
, 9:1, 10 cycles).
+
·
corresponding dication. The next irreversible oxidation
peak indicates the formation of oligomers on the electrode
surface. Based on these data, it was revealed that
compounds 12 and 13 have sufficiently deep HOMO
levels, values of which are significantly below the air
oxidation threshold (about –5.2 eV), which in turn provides
a good air stability for the molecules and increases the open
the formation of the radical cation (TPA ), which rapidly
dimerizes to form tetraphenylbenzidine. The next peak
+·
corresponds to the formation of radical cation (TPB ),
2+
further oxidation of which leads to a dication (TPB ). Its
formation is evidenced by the appearance of a third peak on
the CV curve, with such separation of the peaks
characteristic only for the first wave of oxidation–
reduction. The first oxidation peak always remains
reversible. In our case, three reversible oxidation peaks are
observed on the CV curves for compounds 14, 15 (Table 2),
with the latter two becoming gradually smoothed under
multiple potential scans. The first reversible oxidation peak
1
8,42
circuit voltage (Voc) of the solar cell.
It is known that structures containing triphenylamine
TPA) fragment are electrochemically active, and that
(
triphenylamine dimerizes with the loss of two protons to
form N,N,N',N'-tetraphenyl-4,4'-diaminobiphenyl (tetraphenyl-
1
benzidine, TPB) as
a
result of electrochemical
(Eox ) describes the formation of the corresponding radical
oxidation.4
3,44
Three peaks on the anode curve and two
cation of triphenylamine, which is stable presumably due to
the presence of a conjugated chain in the structure of
molecules. This cation radical further dimerizes to form a
peaks on the cathode curve usually present on a CV curve
of triphenylamine. The first oxidation peak corresponds to
Table 2. The values of oxidation and reduction potentials, ionization potentials and electron affinities of compounds 12–15
+
–
(
MeCN–CH
2
Cl
2
, 9:1, bulk electrolyte Et
4
N ClO
4
)
Com-
pound
ox1*, В
ox2*, В
ox3*, В
red1**, В
red2**, В
red3**, В
E
oxonset, В HOMO, eV LUMO, eV
E
E
E
E
E
E
1
1
1
1
2
3
4
5
E
0.68
0.87
1.03
0.99
0.93
1.33
1.23
1.31
1.61
1.70
1.65
1.71
0.48
0.65
0.97
0.87
0.75
1.21
1.19
1.25
–
1.32
1.17
0.91
0.81
–5.71
–5.56
–5.30
–5.20
–3.28
–3.31
–3.13
–3.15
–
1.61
1.67
1–3
*
ox – value of oxidation wave potential.
1–3
*
* Ered – value of reduction wave potential.
3
83

Chemistry of Heterocyclic Compounds 2016, 52(6), 379–387
Fig. 6. 2D-STM image of surface films of compounds 12–15, scan size 1×1 μm.
substituted tetraphenylbenzidine, and the following two
a Shimadzu UV-2600 spectrophotometer, 10-mm cuvettes,
–5
peaks are related to oxidation of the TPB fragment (cation
radical, dication).
solvent – abs. CHCl
spectra were recorded on
spectrofluorometer. Excitation wavelength 220 nm, cuvette
dimensions 10×10 mm, solvent – abs. CHCl , concentra-
tion 10–5 М. H NMR spectra were acquired on a Varian
Mercury plus300 spectrometer (300 MHz) in CDCl
3
, concentration 10 М. Fluorescence
a
Shimadzu RF-5301
Thin films of compounds 12–15 were obtained on an
ITO substrate by spin coating technique from chloro-
benzene solution (5 mg/ml). The structure of the films was
studied using scanning tunneling microscopy (NTEGRA
Prima – Modular (AFM, STM) system). All measurements
were carried out under standard conditions; a voltage of
3
1
3
,
internal standard hexamethyldisilazane (0.037 ppm). Signals
of the carbazole protons are denoted as Cz, signals of the
thiophene protons as Th. Mass spectra were recorded on a
Agilent GC 6890N MSD 5975B LC-MS system, EI
ionization (70 eV). Elemental analysis was performed on a
CHNS-932 apparatus (LECO Corporation), chlorine
content was determined using the Schöniger method.45
Monitoring of the reaction progress and assessment of the
purity of synthesized compounds were done by TLC
(Sorbfil). Separation of mixtures and purification of target
compounds were performed by column chromatography on
silica gel (Lancaster, Silica gel 60, 0.060–0.200 mm), the
diameter of the column and the height of the silica gel layer
were determined by the amount of the substance to be
purified. The method of cyclic voltammetry was used to
perform the electrochemical studies of the synthesized
compounds. The measurements were performed on a
Gamry Interface1000 potentiostat in a three-electrode cell
with carbon pyroceramics working electrode, a platinum
auxiliary electrode, and silver chloride reference electrode.
Solutions of the samples in 10 ml of a mixture of abs.
0
.1 V was applied on the scanning probe (palladium wire)
and a current of ~0.5 nA was maintained. Examples of the
obtained images demonstrates a sufficiently smooth surface
for the obtained films, without large crystalline domains.
The average particle size was 30 nm (Fig. 6).
To conclude, we have synthesized novel substituted
alkylidene malononitrile structures which can be described as
Cz–C
6
H
4
–Th
n
–CH=C(CN)
2
and Ph
2
N–C
6
H
4
–Th
n
–C(Ме)=C(CN)
2
(Cz = 9H-carbazol-9-yl, Th = thiophen-2-yl, n = 1, 2) and
which can be considered as potential materials for bulk-
heterojunction solar cells. The results of quantum-chemical
calculations of the energies of frontier molecular orbitals
were corroborated by experimental data, according to
which the synthesized compounds have a narrow band gap
of 2.43-2.05 eV. It was found that the resulting compounds
have good film-forming properties, yielding thin films of
good quality with a smooth surface.
Experimental
MeCN and CH
2
Cl
2
, 9:1, were used in the studies,
+
–
supporting electrolyte 0.1 М Et
4
N ClO
4
. Studies of the
IR spectra were registered on a Specord 75 IR
structure of the films was done on the NTEGRA Prima
scanning probe microscope, in scanning tunneling
microscopy mode. Deposition of the film was done in an
spectrometer in CHCl (compounds 13–15) or in petroleum
3
jelly (remaining compounds). UV spectra were recorded on
3
84

Chemistry of Heterocyclic Compounds 2016, 52(6), 379–387
argon-filled sealed glove box Nitrogen Glove Box
PlasLabs, spin coater SPIN 12000.
J = 9.0, H-2,6 C
6
H
4
); 7.61 (1H, d, J = 3.9, Н-3 Th); 10.11
(1H, d, J = 6.9, CHO). Mass spectrum, m/z (Irel, %): 417 [M
37
+
37
+
35
+
Compounds 1, 2, 7–9 were synthesized according to
( Cl)] (42), 416 [M( Cl)+H] (30), 415 [M( Cl)] (100),
382 (10), 381 (31), 380 (94), 352 (18), 351 (27), 273 (13),
190 (48), 176 (12), 168 (13), 167 (22), 139 (11), 77 (13).
1-{5'-[4-(Diphenylamino)phenyl]-2,2'-bithiophen-5-yl}-
ethanone (11). 3-Aryl-3-chloroprop-2-enal (10) (3.54 g,
1
8,27
published methods.
Synthesis of compounds 5, 6 (General method). A
mixture of bromo-substituted aldehyde 3, 4 (0.02 mol),
4
-(9Н-carbazol-9-yl)phenylboronic acid (2) (5.74 g, 0.02 mol),
Pd(PPh
3
)
4
catalyst (3% by weight of bromo-substituted
CO (10 ml)
8.5 mmol) was added to a solution of Na
2
S·9H O (2.00 g,
2
aldehyde), PhH (20 ml), and 2 M aqueous Na
2
3
8.5 mmol) in DMF (15 ml). The reaction mixture was
stirred at 60°C for 3 h, then chloroacetone (0.7 ml,
8.5 mmol) was added dropwise and stirring at 60°C
was heated under reflux under argon for 24 h. Upon
completion of the reaction (monitoring by TLC), the
mixture was cooled to room temperature and the organic
phase was separated. The aqueous phase was extracted
continued for 2 h. A solution of K
2
CO (1.20 g, 8.5 mmol) in
3
Н О (1 ml ) was added. The mixture was stirred at 60°C for
2
with CH
concentrated. The residue was purified by column
chromatography (eluent CH Cl ).
-[4-(9Н-Carbazol-9-yl)phenyl]thiophene-2-carbaldehyde
5). Yield 0.57 g (81%), yellow-green crystals, mp 194–
2 2
Cl , the organic phases were combined and
10 min, then cooled to room temperature, and poured in
water. The formed precipitate was filtered off, washed with
2
2
water, and purified by chromatography (eluent CH
2
2
Cl ).
5
Yield 2.9 g (76%), dark-yellow crystals, mp 149–150°С. IR
–1 1
(
1
spectrum, ν, cm : 1647 (C=O). H NMR spectrum, δ, ppm
(J, Hz): 2.54 (3H, s, COCH ); 7.05 (1H, d, J = 3.6, Н-4'
Th); 7.06 (2H, d, J = 8.7, H-3,5 C ); 7.10−7.14 (6H, m,
–
1
1
96°C. IR spectrum, ν, cm : 1696 (C=O). H NMR
3
spectrum, δ, ppm (J, Hz): 7.30 (2H, t, J = 9.0, H-3,6 Cz);
6
H
4
7
.39 (2H, d, J = 9.0, H-1,8 Cz); 7.44 (2H, t, J = 9.0, H-2,7
Cz); 7.46 (1H, d, J = 4.6, H-3 Th); 7.64 (2H, d, J = 9.6,
H-2,6 C ); 7.77 (1Н, d, J = 4.3, H-4 Th); 7.88 (2H, d,
); 8.13 (2Н, d, J = 8.6, H-4,5); 9.92
H-2,2',4,4',6,6' Ph); 7.15 (1H, d, J = 4.2, Н-3' Th); 7.27
(4H, t, J = 6.6, H-3,3',5,5' Ph); 7.29 (1H, d, J = 3.6, H-4 Th);
6
H
4
7.44 (2H, d, J = 8.7, H-2,6 C
6
H ); 7.57 (1H, d, J = 4.2, Н-3 Th).
4
J = 9.3, H-3,5 C
6
H
4
Found, %: C 74.54; H4.63; N 3.16; S 14.13. C28
Calculated, %: C74.47; H 4.69; N 3.10; S 14.20.
H
21NOS .
2
+
(
(
1Н, s, CHO). Mass spectrum, m/z (Irel, %): 354 [M+H]
+
26), 353 [M] (100), 280 (11), 176 (12), 140 (9). Found,
Synthesis of compounds 12−15 (General method). A mix-
%
: C 78.08; H 4.31; N 3.99; S 9.13. C23
H
15NOS.
ture of aldehyde 5, 6 or ketone 9, 11 (5 mmol), CH
(0.33 g, 5 mmol), glacial AcOH (0.12 ml), and NH
(40 mg) in PhH (5 ml) was heated under reflux for 10 h in
the Dean–Stark apparatus. Additional CH (CN) (0.33 g,
5 mmol), AcOH (0.12 ml), and NH OAc (40 mg) were
2
(CN)
4
2
Calculated, %: C 78.16; H 4.28; N 3.96; S 9.07.
-{5'-[4-(9Н-Carbazol-9-yl)phenyl]-2,2'-bithiophen-
-yl}-2-carbaldehyde (6). Yield 0.65 g (75%), yellow-
OAc
2
5
2
2
–1
orange powder, mp 141–144°С. IR spectrum, ν, cm : 1662
4
1
(
C=O). H NMR spectrum, δ, ppm (J, Hz): 7.17 (1H, d,
added, and heating under reflux continued for 10 h. The
mixture was then cooled to room temperature, diluted with
EtOAc (30 ml), washed with H O (25 ml), followed by
J = 4.6, H-4' Th); 7.30 (2H, t, J = 8.6, H-3,6 Cz); 7.33 (2H,
d, J = 9.0, H-1,8 Cz); 7.35 (1Н, d, J = 4.0, H-3' Th); 7.38
2
(
7
1H, d, J = 4.0, H-4 Th); 7.44 (2H, t, J = 8.6, H-2,7 Cz);
saturated aqueous NaCl (4 ml), and dried over anhydrous
Na SO . The extract was filtered and concentrated under
reduced pressure. The final product was separated by
.62 (2H, d, J = 9.3, H-2,6 C
6
H
4
); 7.70 (1H, d, J = 4.3, H-3
); 8.14 (2H, d,
2
4
Th); 7.83 (2H, d, J = 10.0, H-3,5 C
6
H
4
J = 8.3, H-4,5 Сz); 9.88 (1H, s, CHO). Mass spectrum, m/z
column chromatography, eluent CH
2
2
Cl .
+
+
+
(
(
I
rel, %): 437 [M+2H] (13), 436 [M+H] (31), 435 [M]
100), 217 (10), 181 (11). Found, %: C 74. 49; H 3.90;
. Calculated, %: C 74.45;
2-({5-[4-(9H-Carbazol-9-yl)phenyl]thiophen-2-yl}-
methylidene)malononitrile (12). Yield 1.28 g (64%),
–1
N 3.27; S 14.65. C27
H
17NOS
2
orange powder, mp 258–260°С. IR spectrum, ν, cm : 2217
(С≡N). UV spectrum, λmax, nm (log ε): 294 (4.18), 327
H 3.93; N 3.22; S 14.72.
-Chloro-3-{5-[4-(diphenylamino)phenyl]thiophen-2-yl}-
3
(3.95), 341 (4.03), 433 (4.41). Fluorescence spectrum, λmax,
1
prop-2-enal (10). POCl
3
(1.15 ml, 12 mmol) was slowly
nm: 545. H NMR spectrum, δ, ppm (J, Hz): 7.32 (2H, t,
J = 9.0, H-3,6 Cz); 7.41 (2H, d, J = 9.0, H-1,8 Cz); 7.46
(2H, t, J = 9.6, H-2,7 Cz); 7.53 (1H, d, J = 4.6, H-4 Th);
added to DMF (1.30 ml, 17 mmol) at 0°С, the mixture was
stirred at 0°С for 10 min. Then a solution of ketone 9 (3.69 g,
1
0 mmol) in DMF (15 ml) was added dropwise, and the
7.77 (1H, d, J = 4.6, H-3 Th); 7.83 (1H, s, CH=С(CN)
(2H, d, J = 9.3, H-2,6 C ); 7.96 (2H, d, J = 9.6, H-3,5
2
); 7.93
reaction mixture was stirred at 60°С for 3 h. After cooling
6
H
4
the mixture, 10% aqueous NaOAc was added until pH 4.
C
6
H ); 8.14 (2H, d, J = 8.3, H-4,5 Cz). Found, %: C 77.70;
4
3
-Aryl-3-chloroprop-2-enal 10 that separated was filtered
H 3.70; N 10.41; S 8.02. C26
C 77.78; H 3.77; N 10.47; S 7.99.
H
15
3
N S. Calculated, %:
off, washed with water. An analytical sample was purified
by chromatography (eluent CH Cl ), the rest used in the
synthesis without additional purification. Yield 1.33 g
80%), slowly crystallizing dark-red mass, mp 96–97°С. IR
2
2
2-({5'-[4-(9Н-Carbazol-9-yl)phenyl]-2,2'-bithiophen-
5-yl}methylidene)malononitrile (13). Yield 1.28 g (53%),
–1
(
thick orange-red mass. IR spectrum, ν, cm : 2216 (С≡N). UV
spectrum, λmax, nm (log ε): 295 (4.20), 329 (4.08), 342
(4.05), 450 (4.54). Fluorescence spectrum, λmax, nm: 599.
–1
1
spectrum, ν, cm : 1661 (CHO). H NMR spectrum, δ, ppm
J, Hz): 6.54 (1H, d, J = 6.6, C(Cl)=CH–CHO); 7.04 (2H,
d, J = 8.7, H-3,5 C ); 7.09 (2H, t, J = 7.5, H-4,4' Ph);
.11 (4H, d, J = 8.7, H-2,2',6,6' Ph); 7.20 (1H, d, J = 4.2,
Н-4 Th); 7.28 (4H, t, J = 7.2, H-3,3',5,5' Ph); 7.44 (2H, d,
(
1
6
H
4
H NMR spectrum, δ, ppm (J, Hz): 7.19 (1H, d, J = 4.3,
7
H-4' Th); 7.25 (2H, d, J = 9.6, H-3,6 Cz); 7.31 (2H, d,
J = 9.0, H-1,8 Cz); 7.33 (1H, d, J = 4.0, H-3' Th); 7.41 (1H,
3
85

Chemistry of Heterocyclic Compounds 2016, 52(6), 379–387
9. Kumar, C. V.; Cabau, L.; Koukaras, E. N.; Sharma, G. D.;
d, J = 4.3, H-4 Th); 7.45 (2H, d, J = 9.0, H-2,7 Cz); 7.47
1H, d, J = 4.6, H-3 Th); 7.63 (2H, d, J = 9.6, H-3,5 C );
.77 (1H, s, CH=С(CN) ); 7.84 (2H, d, J = 9.3, H-2,6
(
6
H
4
Palomares E. Org. Electron. 2015, 26, 36.
0. Murali, M. G.; Rao, A. D.; Yadav, S.; Ramamurthy, P. C.
Polym. Chem. 2015, 6, 962.
1
1
1
1
1
1
7
2
C
6
H ); 8.15 (2H, d, J = 8.6, H-4,5 Cz). Found, %: C 74.48;
4
1. Yassin, A.; Rousseau, T.; Leriche, P.; Cravino, A.; Roncali, J.
Sol. Energy Mater. Sol. Cells 2011, 95, 462.
2. Zhang, W.; Tse, S. C.; Lu, J.; Tao, Y.; Wong, M. S. J. Mater.
Chem. 2010, 20, 2182.
H 3.50; N 8.61; S 13.20. C30
C 74.51; H 3.54; N 8.69; S 13.26.
H
17
N
3
S . Calculated, %:
2
2
-(1-{5-[4-(Diphenylamino)phenyl]thiophen-2-yl}-
ethylidene)malononitrile (14). Yield 0.63 g (63%), thick
3. Jadhav, T.; Misra, R.; Biswas, S.; Sharma, G. D. Phys. Chem.
Chem. Phys. 2015, 17, 26580.
–
1
dark-red mass. IR spectrum, ν, cm : 2206 (C≡N). UV
spectrum, λmax, nm (log ε): 307 (5.00), 465 (5.21).
4. Li, P.; Tong, H.; Ding, J.; Xie, Z.; Wang, L. J. Mater. Chem.
A 2013, 1, 8805.
1
Fluorescence spectrum, λmax, nm: 611. H NMR spectrum,
δ, ppm (J, Hz): 2.67 (3H, s, CH ); 7.04 (2H, d, J = 8.7,
3
5. Shiau, S.-Y.; Chang, C.-H.; Chen, W.-J.; Wang, H.-J.; Jeng, R.-J.;
Lee, R.-H. Dyes Pigm. 2015, 115, 35.
H-3,5 C
J = 8.7, H-2,2',6,6' Ph); 7.27−7.32 (4H, m, H-3,3',5,5' Ph);
.32 (1H, d, J = 3.6, H-4 Th); 7.50 (2H, d, J = 8.7, H-2,6
6
H
4
); 7.12 (2H, t, J = 6.6, H-4,4' Ph); 7.13 (4H, d,
16. Feng, H.-F.; Fu, W.-F.; Li, L.; Yu, Q.-C.; Lu, H.; Wan, J.-H.;
Shi, M.-M.; Chen, H.-Z.; Tan, Z.; Li, Y. Org. Electron. 2014,
15, 2575.
7
C
6
H ); 8.00 (1H, d, J = 4.2, H-3 Th). Found, %: C 77.64;
4
H 4.54; N 10.10; S 7.58. C27
H 4.59; N 10.06; S 7.68.
H
19
N
3
S. Calculated, %: C 77.67;
17. Li, M.; Ni, W.; Feng, H.; Wan, X.; Liu, Y.; Zuo, Y.; Kan, B.;
Zhang, Q.; Chen, Y. Org. Electron. 2015, 24, 89.
1
8. Liu, L.; Li, H.; Zhang, X.; Wei, Y.; Li, J.; Tian, W. J. Mater.
2-(1-{5'-[4-(Diphenylamino)phenyl]-2,2'-bithiophen-5-yl}-
Sci. 2014, 49, 5279.
ehylidene)malononitrile (15). Yield 0.51 g (57%), thick
–
1
19. Li, Z.; Dong, Q.; Xu, B.; Li, H.; Wen, S.; Pei, J.; Yao, S.; Lu, H.;
Li, P.; Tian, W. Sol. Energy Mater. Sol. Cells 2011, 95, 2272.
20. Deng, D.; Shen, S.; Zhang, J.; He, C.; Zhang, Z.; Li, Y. Org.
Electron. 2012, 13, 2546.
maroon mass. IR spectrum, ν, cm : 2224 (C≡N). UV
spectrum, λmax, nm (log ε): 303 (5.20), 357 (5.11), 477
1
(5.21). Fluorescence spectrum, λmax, nm: 656. H NMR
spectrum, δ, ppm (J, Hz): 2.67 (3H, s, CH
J = 9.0, H-3,5 C ); 7.06 (1H, d, J = 3.6, H-4' Th);
.10−7.14 (6H, m, H-2,2',4,4',6,6' Ph); 7.18 (1H, d, J = 4.2,
H-3' Th); 7.27 (4H, t, J = 6.6, H-3,3',5,5' Ph); 7.32 (1H, d,
J = 3.9, H-4 Th); 7.45 (2H, d, J = 8.4, H-2,6 C ); 7.96
1H, d, J = 4.2, H-3 Th). Found, %: C 74.45; H 4.30;
N 8.47; S 12.78. C31 . Calculated, %: C 74.52;
H 4.24; N 8.41; S 12.83.
3
); 6.93 (2H, d,
2
1. Kwon, J.; Lee, W.; Kim, J.-Y.; Noh, S.; Lee, C.; Hong, J.-I.
New J. Chem. 2010, 34, 744.
6
H
4
7
22. Bakiev, A. N.; Gorbunov, A. A.; Lunegov, I. V.; Shklyaeva, E. V.;
Abashev, G. G. Butlerov Commun. 2015, 42(4), 66.
6
H
4
[Butlerovskie soobshcheniya 2015, 66.]
(
23. Zhang, X.; Guo, F.; Li, X.; He, J.; Wu, W.; Agren, H.; Hua, J.
NANO 2014, 9(5), 1440009.
24. Ooyama, Y.; Harima, Y. ChemPhysChem 2012, 13, 4032.
H
21
N
S
3 2
2
2
2
5. Amaladass, P.; Clement, J. A.; Mohanakrishnan, A. K.
Tetrahedron 2007, 63, 10363.
6. Huo, L.; Li, Z.; Guo, X.; Wu, Y.; Zhang, M.; Ye, L.; Zhang, S.;
Hou, J. Polym. Chem. 2013, 4, 3047.
The work was supported by the Ministry of Education
and Science of the Russian Federation (project 012 011
4
61 916) and the Russian Foundation for Basic Research
7. Krucaite, G.; Tavgeniene, D.; Volyniuk, D.; Grazulevicius, J. V.;
Liu, L.; Xie, Z.; Zhang, B.; Grigalevicius, S. Synth. Met.
(
grants 14-03-00341a, 14-03-96003r_ural_a). Instru-
mental investigations were carried out on devices acquired
at the expense of the Program for the development of
national research universities.
2
015, 203, 122.
2
8. Palai, A. K.; Kumar, A.; Sim, K.; Kwon, J.; Shin, T. J.; Jang, S.;
Cho, S.; Park, S.-U.; Pyo, S. New J. Chem. 2016, 40, 385.
9. Hari, D. P.; Schroll, P.; König, B. J. Am. Chem. Soc. 2012,
2
1
34, 2958.
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