J Fluoresc

DOI 10.1007/s10895-015-1565-6

ORIGINAL PAPER

Synthesis, Photophysical and Redox Properties

of the D–π–A Type Pyrimidine Dyes Bearing
the 9-Phenyl-9H-Carbazole Moiety
Egor V. Verbitskiy 1,2 & Aleksandr V. Schepochkin 1 & Nadezhda I. Makarova 3 &
Igor V. Dorogan 3 & Anatoly V. Metelitsa 3 & Vladimir I. Minkin 3,4 & Sergey A. Kozyukhin 5 &
Victor V. Emets 6 & Vitaly A. Grindberg 6 & Oleg N. Chupakhin 1,2 &
Gennady L. Rusinov 1,2 & Valery N. Charushin 1,2

Received: 10 January 2015 / Accepted: 23 March 2015

# Springer Science+Business Media New York 2015

Abstract Novel donor-π-acceptor dyes bearing the pyrimi- device fabrication study. The experimental and calculation
dine unit as an electron-withdrawing group have been synthe- data show that all of the dyes can be regarded as potentially
sized by using combination of two processes, based on the good photosensitizers for dye-sensitized solar cells.
microwave-assisted Suzuki cross-coupling reaction and nu-
cleophilic aromatic substitution of hydrogen. Spectral proper- Keywords Pyrimidine . Carbazole . Nucleophilic aromatic
ties of the obtained dyes in six aprotic solvents of various substitution of hydrogen . Solvatochromism . Dye-sensitized
polarities have been studied by ultraviolet–visible and fluores- solar cells
cence spectroscopy. In contrast to the absorption spectra, fluo-
rescence emission spectra displayed a strong dependence from
their solvent polarities. The nature of the observed long wave-
length maxima has been elucidated by means of quantum Introduction
chemical calculations. The electrochemical properties of these
dyes have been investigated by using cyclic voltammetry, Solvatochromism can be defined as the phenomenon, where-
while their photovoltaic performance was evaluated by a by a compound, being dissolved in various solvents, exhibits
different colors due to a change in absorption or emission
spectra of the molecule [1]. Solvatochromic D–π–A charge
Electronic supplementary material The online version of this article
(doi:10.1007/s10895-015-1565-6) contains supplementary material, transfer dyes have received a considerable attention due to a
which is available to authorized users. growing fundamental interest in photochemistry and their ap-
plication as environmental probes [1, 2]. These dyes attract
* Egor V. Verbitskiy have been paid much attention because of their use for deter-
[email protected] mination of solvent polarity [3], as well as their potential ap-
plication as colorimetric chemosensors for volatile organic
1
I. Postovsky Institute of Organic Synthesis, Ural Branch of the compounds [4, 5]. Charge transfer dyes have also been devel-
Russian Academy of Sciences, S. Kovalevskoy Str., 22, oped for use as photo- (PL) and electroluminescent (EL) ma-
Ekaterinburg 620137, Russia terials in dye lasers [6, 7], sensors [8], switchable viscosity
2
Ural Federal University, Mira St. 19, Ekaterinburg 620002, Russia probes [9], dual-ion-switched molecular brakes [10], dye-
3
Institute of Physical and Organic Chemistry, Southern Federal sensitized solar cells (DSSCs) [11–13] and optical light emit-
University, Stachki Av., 194/2, 344090 Rostov on Don, Russia ting diodes (OLEDs) [14].
4
Southern Scientific Center of the Russian Academy of Sciences, Pyrimidine is a highly π-deficient heterocyclic system, and
Chekhov St., 41, 344006 Rostov on Don, Russia its fragment can be used as an electron-withdrawing part in
5
Kurnakov Institute of General and Inorganic Chemistry, RAS, push-pull structures. The ability of both nitrogen atoms of the
Moscow 119991, Russia pyrimidine ring for protonation, hydrogen bond formation and
6
Frumkin Institute of Physical Chemistry and Electrochemistry, RAS, chelation are also of great importance, since pyrimidine deriv-
Moscow 119071, Russia atives can be used for the formation of supramolecular
 J Fluoresc

assemblies. In addition, π-conjugated compounds bearing the studies, and quantum calculations show that all compounds
pyrimidine fragment have been studied as promising candi- are potentially good photosensitizers for dye-sensitized solar
dates to obtain functional photoelectric materials, due to the cells.
intriguing structural and electronic properties of the pyrimi-
dine ring [15–22]. During the last decade, hundreds of pyrim-
idine chromophores have been designed. In particular, numer- Experimental Section
ous aryl substituted pyrimidines have been studied as fluores-
cent dyes [23–25]. Moreover, it should be noted that arylvinyl General Information
pyrimidines are now considered as well established structures
of two-photon absorption dyes [26–28]. Some pyrimidine de- All reagents and solvents were purchased from commercial
rivatives exhibit also the second order nonlinear optical prop- sources and dried by using standard procedures before use. 1,
erties [28–31]. 4-Dioxane and H2O for the microwave-assisted cross-cou-
It has been shown that combinations of the pyrimi- pling reaction were deoxygenated by bubbling argon for 1 h.
dine fragment with triphenylamine or carbazole units 9H-Carbazole-9-(4-phenyl) boronic acid pinacol ester (1) and
can give materials with excellent fluorescence proper- titanium (IV) oxide, anatase (nanopowder, <25 nm particle
ties. Indeed, elementary pyrimidine-triphenylamine (I) size) were purchased from Sigma-Aldrich. 4-(5-
and pyrimidine-carbazole (II) dyads have been obtained Bromothiophen-2-yl) pyrimidine (2a), 4-[5-(4-bromophenyl)
and used as luminescent materials, exhibiting good solv- thiophen-2-yl] pyrimidine (2b) and 4-(5′-bromo-[2,2′]
ability, film forming, high stability, and quantum effi- bithiophenyl-5-yl) pyrimidine (2d) were prepared according
ciency (Fig. 1) [32, 33]. In addition, diphenyl-(4- to the earlier reported procedure [13].
pyrimidin-4-yl)-amine (I) was examined as a fluorescent Melting points were determined on Boetius combined
ratiometric chemosensor for Hg 2+ [34]. Recently, we heating stages and were not corrected. Elemental analysis
have obtained six donor-π-acceptor organic dyes (IIIa-c was carried on a Eurovector EA 3000 automated analyzer.
1
and IVa-c), bearing the pyrimidine anchoring group as H and 13C NMR spectra were recorded on an AVANCE-
potentially good photosensitizers for dye-sensitized solar 500 instruments using Me4Si as an internal standard. The
cells [13]. GC-MS analysis of all samples was carried out using an
In continuation of this work we have elucidated Agilent GC 7890A MS 5975C Inert XL EI/CI GC-MS spec-
solvatochromic properties of three pigments (3a–c) with 9- trometer with a quadrupole mass-spectrometric detector with
phenyl-9H-carbazole (donor) and pyrimidine (acceptor) frag- electron ionization (70 eV), and scan over the total ionic cur-
ments linked to each other through thiophenyl, 2- rent in the range m/z 20÷1000 and a quartz capillary column
phenylthiophenyl and 2,2′-bithiophenyl groups (Scheme 1). HP-5MS (30 m×0.25 mm, film thickness 0.25 mm). Helium
The static and time-dependent density functional theory served as a carrier gas, the split ratio of the flow was 1: 50, and
(TDDFT) calculations in ground and excited states have been the consumption through the column was 1.0 mL min−1; the
used to analyze the solvatochromism observed in various sol- initial temperature of the column was 40 °C (storage 3 min),
vents. The data derived from optical and electrochemical programming rate was 10 °C min−1 to 290 °C (storage

Fig. 1 Molecular structures of N N

triphenylamine and carbazole N N

dyes containing the pyrimidine N N
ring as an electron-withdrawing I II
H3C
group

N
N
N
S N
N S
N S S
N N
N
IIIa
IIIb IIIc

N
N CH3
N CH3 N
S N S
S S N
N N
N
IVa IVb IVc H3C
J Fluoresc

Scheme 1 Synthesis of the

9-phenyl-9H-carbazole-π-linker- N
pyrimidine dyes 3a–c S
N Br N
2a N
S
N

3a
N Br
S N
N N

K2CO3, Pd(PPh3)4, MW 2b
N
1,4-Dioxane-H2O S
N
B
O O 3b
N
H3C CH S
H3C CH3 3 N S Br
1 2c N
S
S N
N

3c

20 min), the temperature of the evaporator was 250 °C, the couple (Fc/Fc+), which has the known oxidation potential of +
temperature of the source was 230 °C, the temperature of the 4.8 eV. The HOMO energy values were estimated from the
quadrupole was 150 °C, and the temperature of the transition onset potentials (Eoxonset) of the first oxidation event according
chamber was 280 °C. Solutions of the samples with a concen- to the following equation:
tration of 3–4 mg mL−1 were prepared in THF. Samples of the  
obtained solutions (1 mL) were analyzed. EHOMO ðeVÞ ¼ – Eox onset – E1=2 ð Fc= FcþÞ þ 4:8
Column chromatography was carried out using Alfa Aesar
where E1/2(Fc/Fc+) is the half-wave potential of the Fc/Fc+
silica gel 0.040–0.063 mm (230–400 mesh), eluting with ethyl
couple against the Ag/Ag+ electrode.
acetate-hexane. The progress of reactions and the purity of
UV/vis spectra were recorded for a 2×10−5 M solution with
compounds were checked by TLC on Sorbfil plates
Varian Cary 100 spectrophotometer. Photoluminescent spec-
(Russia), in which the spots were visualized with UV light
tra were recorded for a 1×10−6 M solution on a Varian Cary
(λ 254 or 365 nm).
Eclipse fluorescence spectrophotometer. UV/vis and fluores-
Microwave experiments were carried out in a Discover
cence spectra were recorded using standard 1 cm quartz cells
unimodal microwave system (CEM, USA) with a working
at room temperature. Stokes shifts were calculated consider-
frequency of 2.45 GHz and the power of microwave radiation
ing the lowest energetic absorption band.
ranged from 0 to 300 W. The reactions were carried out in a
Comparative study of the photostability of the obtained
10 mL reaction tube with the hermetic Teflon cork. The reac-
compounds and commercial colorant POPOP (1,4-bis (5-
tion temperature was monitored using an inserted IR sensor
phenyloxazol-2-yl) benzene) («Alfa Aesar») has been per-
for the external surface of the reaction vessel.
formed. Toluene solutions of the novel dyes and POPOP were
irradiated with UV light at wavelength 365 nm for 1 h. Initial
Redox and Spectroscopic Properties optical density of all solutions at wavelength 365 nm was
equal to the same value (0.102). Fluorescence spectra of the
Cyclic voltammetry was carried out on a Metrohm Autolab dyes were recorded with 10 min interval between exposures,
PGSTAT128N potentiostat with a standard three-electrode and their intensity were fixed at the maximum of the band.
configuration. Typically, a three electrodes cell equipped with Photolysis of the solutions was carried out using BNewport^
a glass carbon working electrode, Ag/AgNO3 (0.01 M in an- system on the basis of a mercury lamp (200 W) with a set of
hydrous acetonitrile) reference electrode, and a glass carbon interference filters. The intensity of the optical radiation deter-
rod counter electrode was employed. The measurements have mined by the optical power meter BNewport 2935^ at 365 nm
been carried out in anhydrous dichloromethane with was equal to 3.2×1016 photon·s−1.
tetrabutylammonium tetrafluoroborate (0.1 M), as the IR spectra of the dye powders and dyes adsorbed on
supporting electrolyte under an argon atmosphere at a scan TiO2 nanoparticles were recorded on a Spectrum One
rate of 100 mV/s. The potential of Ag/AgNO3 reference elec- Fourier transform IR spectrometer (Perkin Elmer)
trode was calibrated by using the ferrocene/ferrocenium redox equipped with a diffuse reflectance attachment (DRA)
 J Fluoresc

in the frequency range 420–3600 cm−1. Spectrum pro- (250 W) for 30 min. After that solvent was distilled off in
cessing and band intensity determination were carried vacuo, and the residue was purified by flash column chroma-
out using the special software supplied with the tography (hexane/ethyl acetate, 1:2) to afford the desired
spectrometer. cross-coupling products (3a–c).

Molecular Orbital Calculation

9-[4-(5-Pyrimidin-4-yl-Thiophen-2-yl)-Phenyl]
-9H-Carbazole (3a)
Quantum chemical calculations were performed using the
Gaussian 09 program [35]. The ground and first singlet excit-
The Suzuki cross-coupling reaction of 4-(5-bromothiophen-2-
ed state structures of the pyrimidine dyes were optimized
yl) pyrimidine (2a) with 9H-carbazole-9-(4-phenyl) boronic
using CAM-B3LYP [36] long range corrected functional with
acid pinacol ester (1) (which has been performed according
the 6-311+G(d,p) basis set. CPCM solvation model [37] with
to the general procedure) gave after purification by column
parameters corresponded to toluene (ε=2.38), dichlorometh-
chromatography 149 mg (89 %) of 3a as a yellow solid.
ane (ε=8.93) and DMSO (ε=47.24) was used to account for
Melting point: 213–215 °C. 1H NMR (500 MHz, DMSO-
the solvent. The time depended density functional theory (TD
d6) δ (ppm): 7.32 (ddd, J=7.9, 6.4, 1.6 Hz, 2H), 7.44–7.50
DFT) with state-specific methodology [38] was applied for
(m, 4H), 7.72–7.77 (m, 2H), 7.82 (d, J=4.0 Hz, 1H, H-3′),
calculation of absorption and emission spectra.
8.07–8.09 (m, 3H), 8.18 (d, J=4.0 Hz, 1H, H-4′), 8.27 (d, J=
7.9 Hz, 2H), 8.83 (d, J=5.4 Hz, 1H, H-6), 9.14 (d, J=1.3 Hz,
Fabrication of DSSCs
1H, H-2); 13C NMR (126 MHz, DMSO-d6) δ (ppm): 109.72,
115.25, 120.25, 120.55, 122.86, 126.00, 126.33, 127.27,
We used the photoanodes which were prepared on the
127.32, 130.39, 132.12, 136.92, 139.88, 140.98, 146.93,
TCO22-15 glass (Solaronix). Application of Ti-Nanoxide D/
157.60 (C-6), 157.78 (C-4), 158.75 (C-2); Anal. Calcd for
SP paste (Solaronix), comprising a nanocrystalline titanium
C26H17N3S (403.51): C, 77.39; H, 4.25; N, 10.41. Found: C,
dioxide, was performed by the standard «doctor blade» pro-
77.19; H, 4.05; N, 10.47. FT-IR (DRA, cm−1): 422, 478, 531,
cedure, the thickness of thus obtained titanium dioxide film
569, 622, 629, 642, 662, 725, 752, 771, 806, 834, 854, 914,
was 10 μm. Sensitizing of titanium dioxide was performed by
954, 983, 996, 1016, 1088, 1121, 1172, 1189, 1228, 1287,
soaking photoanodes in ~3·10−4 M methanol solutions of dye
1305, 1319, 1336, 1365, 1386, 1451, 1463, 1479, 1491,
for 24 h. A three electrode photoelectrochemical cell (PECC-
1517, 1537, 1569, 1598, 1777, 1911, 2346, 3024, 3052.
2, Zahner Elektrik) cell was used for the photoelectrochemical
measurements. The photoanode served as the working elec-
trode and a platinum wire with the surface area of 5 cm2 was 9-[4′-(5-Pyrimidin-4-yl-Thiophen-2-yl)-Biphenyl-4-yl]
used as the auxiliary electrode. The voltammetric measure- -9H-Carbazole (3b)
ments were performed with an IPC Pro MF potentiostat under
AM 1.5 global one sun of illumination (100 mW cm−2) pro- The Suzuki cross-coupling reaction of 4-[5-(4-bromophenyl)
vided by a solar simulator (Newport 96000). The illumination thiophen-2-yl] pyrimidine (2b) with 9H-carbazole-9-(4-phe-
power at different distances was determined with a Nova ap- nyl) boronic acid pinacol ester (1) (see the general procedure)
paratus (OPHIR-SPIRICON Inc.). The illuminated gave after purification by column chromatography 115 mg
photoanode area was 1.0 cm2. The illumination was per- (61 %) of 3b as a yellow solid. Melting point: 307–308 °C.
formed from the side of TiO2 photoanode with the adsorbed 1
H NMR (500 MHz, CDCl3) δ (ppm): 7.29–7.33 (m, 2H),
dye. The time dependence of the photoanode and cathode 7.42–7.51 (m, 5H), 7.60 (dd, J=5.4, 1.3 Hz, 1H, H-5), 7.66–
potentials under the open-circuit conditions and the photocur- 7.69 (m, 2H), 7.75–7.88 (m, 7H), 8.17 (d, J=7.8 Hz, 2H), 8.70
rents at the short-circuit potential (transients) were measured (d, J=5.4 Hz, 1H, H-6), 9.17 (d, J=1.3 Hz, 1H, H-2); 13C
under the illumination and at dark. NMR (126 MHz, CDCl3) δ (ppm): 109.28, 114.93, 120.08,
120.36, 123.53, 124.55, 126.01, 126.04, 126.56, 127.46,
General Procedure for the Microwave-Assisted Suzuki 127.73, 128.32, 128.77, 129.10, 133.02, 137.32, 139.27,
Cross-Coupling Reactions 140.33, 140.86, 140.95, 148.75, 157.13, 158.69 (C-6),
159.14 (C-4), 159.17 (C-2); Anal. Calcd for C32H21N3S
A solution of K2CO3 (207 mg, 1.5 mmol) in H2O (3 mL) was (479.61): C, 80.14; H, 4.41; N, 8.76. Found: C, 79.81; H,
added to a mixture of а bromo substituted pyrimidine (2a, 2b 4.27; N, 8.75. FT-IR (DRA, cm−1): 626, 660, 677, 695, 727,
or 2c) (0.5 mmol), 9H-carbazole-9-(4-phenyl) boronic acid 741, 752, 769, 810, 917, 936, 959, 983, 1000, 1020, 1118,
pinacol ester (1) (222 mg, 0.6 mmol) and Pd (PPh3) 4 1148, 1183,1235, 1278, 1317, 1335, 1369, 1385, 1400, 1453,
(58 mg, 10 mol %) in 1,4-dioxane (4 mL). The resulting mix- 1464, 1477, 1502, 1519, 1537, 1573, 1569, 1624, 1643, 1734,
ture was irradiated in a microwave apparatus at 160 °C 1793, 1910, 2926, 3048.
J Fluoresc

Table 1 UV/vis and photoluminescence data of dyes 3a–c in various aprotic solvents

Dye Solvent ET (30)a Absorption λmax (nm)/ε Photoluminescence Stokes shift

(kcal·mol−1) (103 M−1 ·сm−1) ΔνSt (cm−1)
Excitation λmax (nm) Emission λmax (nm) ФFb

3a n-Heptanec 362, 291, 236 363, 291, 236 406, 428 0.62 2994
3b 31.1 353, 292, 233 351, 292, 233 407, 428 0.55 3759
3c 389, 291, 234 390, 291, 234 447, 474 0.07 3336
3a Toluene 366 (29.6), 292 (19.2) 365, 292 429 0.91 4012
3b 33.9 364 (46.6), 293 (24.5) 364, 392 422 0.57 3776
3c 400 (43.2), 293 (22.05) 398, 293 465 0.19 3495
3a Chloroform 366 (33.65), 292 (21.95) 365, 292 467 0.75 5909
3b 39.1 366 (55.2), 293 (29.45) 366, 293 458 0.60 5488
3c 402 (45.85), 293 (22.3) 400, 292 492 0.36 4550
3a Dichloromethane 363 (36.5), 292 (22.65) 364, 292 472 0.74 6362
3b 40.7 363 (57.6), 292 (29.25) 364, 292 462 0.65 5903
3c 399 (45.45), 292 (22.2) 398, 292 494 0.35 4820
3a Acetone 359 (36.7) 360 477 0.71 6891
3b 42.2 361 (39.25) 362 470 0.59 6424
3c 395 (45650) 395 492 0.29 4991
3a DMSO 367 (38.75), 292 (23.65) 365, 292 498 0.65 7168
3b 45.1 368 (46.45), 293 (23.85) 367, 293 500 0.52 7174
3c 405 (46.3), 293 (23.6) 405, 293 512 0.51 5160
a
Dimroth-Reichardt polarity parameter, kcal mol−1 [1]
b
Fluorescence quantum yield determined relative to quinine bisulfate in 0.1 N H2SO4 as standard (ФF =0.52); excitation at 365 nm [39]
c
Poorly soluble

9-[4-(5′-Pyrimidin-4-yl-[2,2′] Bitiophenyl-5-yl)-Phenyl] Results and Discussion

-9H-Carbazole (3c)
Materials Synthesis
The Suzuki cross-coupling reaction of 4-(5′-bromo-[2,2′]
bithiophenyl-5-yl) pyrimidine (2c) with 9H-carbazole-9-(4- The target compounds 3a–c were prepared in good yields
phenyl) boronic acid pinacol ester (1) (see the general proce- according to a procedure described in the previous publication
dure) gave after purification by column chromatography [13]. The starting materials 2a, 2b and 2c were coupled with
76 mg (67 %) of 3c as a yellow solid. Melting point: 245– 9H-carbazole-9-(4-phenyl) boronic acid pinacol ester (1) un-
247 °C. 1H NMR (500 MHz, CDCl3) δ (ppm): 7.28–7.33 (m, der microwave irradiation using 1,4-dioxane/H2O (4:3) as sol-
3H), 7.36 (dd, J=13.0, 3.8 Hz, 2H), 7.42–7.48 (m, 4H), 7.57 vent, K2CO3 and Pd (PPh3) 4, as catalyst. All reactions studied
(dd, J=5.4, 1.2 Hz, 1H, H-5), 7.61–7.64 (m, 2H), 7.72 (d, J= proved to afford the corresponding 9-phenyl-9H-carbazole-π-
4.0 Hz, 1H), 7.83–7.86 (m, 2H), 8.16 (d, J=7.8 Hz, 2H), 8.69 linker-pyrimidine dyes 3a–c in 61–89 % yields within a reac-
(d, J=5.4 Hz, 1H, H-6), 9.15 (d, J=1.2 Hz, 1H, H-2); 13C tion time not exceeding 30 min (Scheme 1).
NMR (126 MHz, CDCl3) δ (ppm): 109.76, 114.85, 120.14, The structural evidence for compounds 3a–c has been ob-
120.36, 123.50, 124.55, 124.75, 126.00, 126.03, 127.04, tained by elucidating their spectral data, including 1H and 13C
127.49, 128.51, 132.78, 136.43, 137.28, 140.24, 140.66, NMR (see Supporting Information), and the data of elemental
142.11, 143.52, 157.07 (C-6), 158.42 (C-4), 159.11 (C-2); analysis.
Anal. Calcd for C30H19N3S2 (485.63): C, 74.20; H, 3.94; N,
8.65. Found: C, 74.22; H, 3.83; N, 8.54. FT-IR (DRA, cm−1): Photophysical and Electrochemical Properties
623, 641, 657, 667, 725, 747, 765, 796, 834, 878, 914, 960,
993, 1017, 1085, 1110, 1120, 1148, 1171, 1230, 1284, 1306, The optical properties of the prepared donor-π-acceptor
1316, 1335, 1365, 1386, 1414, 1451, 1470, 1509, 1530, 1573, (D–π–A) type pyrimidine dyes containing 9-phenyl-9H-
1595, 1624, 1759, 1908, 2927, 3059. carbazole unit 3a–c have been elucidated by UV/vis and
 J Fluoresc

photoluminescence (PL) spectroscopy in six aprotic solvents

with different Dimroth-Reichardt polarity parameter (ET(30)),
notably n-heptane (31.1), toluene (33.9), chloroform (39.1),
dichloromethane (40.7), acetone (42.2) and dimethyl sulfox-
ide (45.1) [1]. The results of these studies are summarized in
Table 1.
The aim of this study was to explore the effect of solvent
polarity on photophysical properties of these fluorophores,
and to correlate these effects to their structures. The pyrimi-
dine dyes 3a–c have been established to show broad absorp-
tion maxima at the region of 353–405 nm (ε = 19200–
45650 M−1 ·сm−1), which can be attributed to intramolecular
charge-transfer excitation from the carbazole moiety to the Fig. 2 Absorption end emission wavelength (λmax) as a function of the
pyrimidine ring (Table 1). The second and third absorption Dimroth-Reichardt polarity parameter for dyes 3a–c
maxima proved to appear at 291–293 and 234–236 nm, re-
spectively. UV–vis spectra for 3a–c in various solvents are
Influence of the structure of dyes 3a–c on the fluorescence
shown in Figs. S1, S2 and S3 (see Supplementary Material).
spectra is similar to that on the absorption spectra. In contrast
The D–π–A type pyrimidine dyes 3a–c bearing the 9-phe-
to the absorption spectra, fluorescence emission spectra exhib-
nyl-9H-carbazole unit exhibited blue-shifted absorption (Δλ=
it a strong dependence from the solvent polarity (Table 1,
21–36 nm in toluene) and fluorescence (Δλ=39–44 nm in
Fig. 3).
toluene) emission spectra in comparison with the recently
The emission bands exhibit the red shifts with increasing of
studied dyes of a similar structure on the basis of pyrimidine
a solvent polarity and they cover a wide spectral range, pro-
linked with the triphenylamine unit [13]. Since the ionization
viding solutions of various colors from blue to green (Fig. 4).
potential of carbazole is higher than that of triphenylamine, it
The observed correlation of the emission band wavelength
can be suggested that a decrease in a donor ability of the D-
with the solvent-dependent ET(30) Dimroth-Reichardt polari-
fragment of dye is the reason of hypsochromic shift. Such
ty parameter (see Fig. 1) is typical for compounds which un-
dependence inherent for the absorption bands which are due
dergo the intramolecular photoinduced electron transfer lead-
to intramolecular charge transfer [40].
ing to a high polarity state which is stabilized by solvent [1,
The structural modification of π-conjugated linker
42].
provides a significant influence on the absorption prop-
The Stokes shifts for 3a–c are enhanced with increasing of
erties of the D–π–A derivatives 3a–c (Table 1). An
solvent polarity from 2994 to 3759 cm−1 in n-heptane to
elongation of π-linker in the D–π–A molecules, such
5160–7174 cm−1 in DMSO (Fig. 5).
as 9-[4-(5′-pyrimidin-4-yl-[2,2′] bithiophenyl-5-yl)-phe-
High values of the Stokes shifts may be due to a remarkable
nyl]-9H-carbazole 3c, by incorporating the second thio-
change in dipole moments of dye molecules in the excited
phene ring leads to a significant shift of the long-
wavelength absorption (Δλmax =27–38 nm) in compari-
son with 3a in all investigated solvents.
On the other hand, incorporation of the phenyl ring in the
dye 3b causes a hypsochromic shift of 9 nm in n-heptane and
2 nm in toluene, or a small bathochromic shift of 2 nm in other
cases in comparison with those observed for compound 3a.
Probably, it may be due to the disarranged π-conjugation in
molecule 3b owing to nonplanar structure of the biphenyl
fragment in solution [41].
It has been found that polarity of solvents exerts a weak
influence on the long-wavelength absorption maxima of com-
pounds 3a–c (Fig. 2). It can be attributed to a small change in
dipole moments of the molecules in the excited Franck-
Condon state.
Effective channel deactivation of electronic excitation en-
ergy of dyes 3a–c is the fluorescence (Table 1, Figs. 3, S4 and
S5). The excitation spectra proved to coincide with the absorp- Fig. 3 Normalized emission spectra (λex =365 nm) of compound 3a in
tion spectra (Table 1). various solvents
J Fluoresc

ΦF

0.9 3a
3b
0.8 3c
0.7

0.6
DMSO
0.5
CH2Cl2
0.4 CHCl3
Acetone
0.3
Toluene
0.2
Heptane
0.1

30 32 34 36 38 40 42 44 46
ET(30) (kcal/mol)
Fig. 6 Fluorescence quantum yield as a function of the Dimroth-
Reichardt polarity parameter for dyes 3a–c
Fig. 4 Solutions photographs of dye 3a in heptane (1), toluene (2),
chloroform (3), dichloromethane (4), acetone (5) end DMSO (6): a With increase in polarity of the solvent quantum yields of
before radiation (no emission); b) during radiation (emission, λex =
365 nm) at room temperature
the photoluminescence can be either reduced (see compound
3a) or increased (compound 3c) (Fig. 6).
To explain the observed behavior, non-radiative deactiva-
state resulted from charge transfer from donor to acceptor tion processes of the excited states should be taken into ac-
fragment, which are accompanied by a compensatory relaxa- count. First of all, improving the efficiency of internal conver-
tion of the solvent molecules [13, 42, 43]. sion results in a decrease in the energy gap S0-S1 of the irra-
An expansion of the π-linker by incorporating the addition- diating structure for compounds 3a–c. On the other hand, an
al thiophene ring leads to a significant bathochromic shift increase in structural flexibility of molecules with incorpora-
Δλ=12–43 nm) of the emission bands in comparison with tion of the thienyl or phenyl fragments into π-linker leads to a
compounds 3a and 3b (Table 1). smaller probability of non-irradiative processes for account of
Quantum yields for fluorescence of dyes 3a–c are strongly appearance of additional vibrational and rotational modes in
dependent on polarity of the solvents and their molecular the molecules. The difference in the character for the depen-
structure, varying from 0.07 to 0.91 (Table 1). Thus, expan- dence of quantum yields for fluorescence of compounds 3a–c
sion of π-linker by incorporating the thiophene or phenyl rings from solvent polarity is a consequence of the impact of the
r e s ul t s in a r e d uc t i on o f qu a nt um y i e l d s o f t h e above mentioned factors, operating in opposite directions with
photoluminescence. increasing a solvent polarity. Probably, decrease of the

Fig. 5 The Stokes shifts as a function of the Dimroth-Reichardt polarity Fig. 7 Fluorescence intensity decay of compounds 3a–c and POPOP
parameter for dyes 3a–c when irradiated with light at 365 nm in toluene
 J Fluoresc

Fig. 8 FTIR spectra of dye

powders and dyes adsorbed on
TiO2 nanoparticles for a 3a, b 3b
and c) 3c

fluorescence efficiency with increasing of the solvent polarity emitting state as a result of intramolecular charge transfer. In
in case of compound 3a is due to a smaller energy gap S0-S1 of case of compounds 3b and 3c the major contribution to the
J Fluoresc

formation of radiative channel for deactivation of electronic Table 2 Electrochemical properties of 9-phenyl-9H-carbazole-π-
pyrimidine 3a–c derivatives
excitation energy belongs to the processes which are connect-
ed with their greater structural flexibility in comparison with Dye Eoxonset a, V EHOMO, eV ELUMOcalc b, eV Eg c, eV
compound 3a. Namely, with increasing of the solvent polarity
the stabilization of coplanar conformation in molecules 3b and 3a 1.03 −5.39 −2.36 3.03
3c takes place. It enhances a probability for intramolecular 3b 1.02 −5.38 −2.33 3.05
charge transfer and forming of radiative state. 3c 0.96 −5.32 −2.63 2.69
All compounds are photostable. Compounds 3a–c show a
Eoxonset – Onset oxidation potential
significantly higher resistance to photodegradation than b
ELUMOcalc =EHOMO +Eg
luminophore POPOP. Irradiation of the solutions 3a–c with c
Eg–Energy gap estimated from the onset of the absorption spectra re-
light at 365 nm within 1 h leads to decreasing of the fluores- corded in CH2Cl2 solution
cence intensity of not more than 5 %, while for POPOP similar
figure is 47 % (Fig. 7).
Along with the certain spectroscopic properties an effective Computational Studies
photosensitizers for dye-sensitized solar cells should possess a
good adsorption to the TiO2 nanoparticles. To prove the coor- To gain insight into the nature of the observed spectral prop-
dinating bonding of dyes 3a–c on TiO2 nanoparticles, we have erties of the dyes 3a–c DFT calculations have been performed.
measured the FTIR spectra of the dye powders and the dyes The obtained results (Table 3, Fig. 10) show that long wave-
adsorbed on TiO2 nanoparticles (Fig. 8). The characteristic length absorption maxima of 3a–c at 366–405 nm are deter-
C=N or C=C bands of the pyrimidine ring were clearly ob- mined by S0-S1 transition with two nearly equal contributions.
served in the range of 1517–1537 and 1569–1573 cm−1. For compounds 3a and 3b the first one (HOMO – LUMO) can
When the dyes 3a–c were adsorbed on the TiO2 surface, the be assigned to intramolecular charge transfer (CT) from the
stretching hands observed at 1517–1537 and 1569–1573 cm−1 carbazole fragment to the rest part of the molecule, while the
have disappeared and a new strong band appeared at 1599– second (HOMO-2 – LUMO) can be characterized as predom-
1600 cm−1, which can be assigned to pyrimidinyl groups co- inately π−π* transitions with a small amount of charge trans-
ordinated to the Lewis acid sites on the TiO2 surface. These fer. For 3c the both contribution (HOMO – LUMO and
consequences are in good agreement with a similar behavior HOMO-1 – LUMO) have a mixed (CT+π−π*) character
of the pyridinyl anchoring group [44–50] and with our previ- associated with a redistribution of electron density within thio-
ous results for the pyrimidinyl anchoring group [13]. phene and phenyl fragments and accompanied by charge
In order to investigate the electron transfer from the excited transfer from carbazole to the pyrimidine moiety.
dye molecule to the conductive band of TiO2, cyclic voltamm- It should be noted that preliminary results of the calcula-
etry (CV) was performed for these dyes in anhydrous CH2Cl2. tions with standard TDDFT hybrid functionals (PBE0,
The CV wave has been found to be not undergoing a substan- B3LYP) noticeably underestimate excitations energy of the
tial modification after repeated scans, thus revealing that all first singlet excited state of 3a–c due to fail to properly ac-
dyes were electrochemically stable under oxidative condi- count for the 1/r dependence of CT excitations. To reduce this
tions. It is worth noting that the presence of a thiophene unit error, we employ a long-range corrected CAM-B3LYP func-
in the π-bridge of 3c decreases its oxidation potential (corre- tional for an improved assessment of CT states. On the other
sponding to the onset of the anodic event) of 0.96 V relative to hand, inclusion of a long-range Hartree-Fock (HF) exchange
dyes 3a and 3b. Since no cathodic behaviour of the dyes can into TDDFT manifested in the lowering of accuracy for
be recorded by CV, their excited state oxidation potentials
(corresponding to the LUMO energy levels) were calculated E (eV)
by adding the energy gap Eg (estimated from the onset of the
-1.5
absorption spectra recorded in CH2Cl2 solutions) to the
-2.0 LUMO -2.33
HOMO energy values (Table 2). It should be noted that the -2.36
-2.63
obtained LUMO for all dyes (−2.33 to −2.63 eV) lay above -2.5
h
-3.0
the TiO2 conduction band edge (~ −4.0 eV) warranting the 3a
-3.5
necessary driving force for an efficient electron transfer pro- TiO2 3b
-4.0 Ecb 3c
cess (Fig. 9). Although the HOMO level of dyes lays at −5.32 -4.0 _ _
I /I3
to −5.39 eV and slightly below experimentally obtained I3−/I−
-4.5 ITO
E
-5.0 -4.7 cb -4.8
redox potential (−4.8 eV), this width of the energy gap is -5.32
-5.5 HOMO -5.39 -5.38
sufficient for dyes regeneration process to take place. Thus,
these compounds can potentially be used as sensitizing agents Fig. 9 Schematic energy diagram for dyes 3a–c, a nanocrystalline TiO2
for DSSC. electrode and I−/I3− redox electrolyte
 J Fluoresc

Table 3 Calculated excitation energies Ecalc (eV) and oscillator strengths f of the S0-S1 transitions of 3a–c according to the TD PCM-CAM-B3LYP/6-
311+G(d,p) calculation in toluene, dichloromethane and DMSO solutions. Eexp (eV) correspond to the observed long wavelength absorption maxima

Dye Toluene Dichloromethane DMSO

Ecalc, eV f Eexp, eV Ecalc, eV f Eexp, eV Ecalc, eV f Eexp, eV

3a 3.526 0.8631 3.397 3.625 0.9974 3.407 3.621 1.0134 3.397

3b 3.708 1.4129 3.407 3.645 1.4074 3.407 3.620 1.4051 3.379
3c 3.360 1.3974 3.116 3.330 1.3973 3.116 3.309 1.3968 3.062

locally excited states. So, systematic overestimation of the Theoretically predicted emission energies (Table 4) are in a
calculated excitation energies (Table 3) is most probably good agreement with the experimental data.
caused by the mixed nature of the S0-S1 transitions containing The visual representation of HOMO and LUMO orbitals
local excitation contributions. Nevertheless, the theoretical es- (Fig. 10) of synthesized dyes clearly support the formation of
timations of the transition energies are in a reasonable agree- push-pull system in molecules. A value for oscillator strengths
ment with the experimental data. ( f ) for the listed dyes (Table 3) implies that they have already
According to the calculation results, electron density redis- a strongly delocalized π-system, but future modifications
tribution in 3a–c upon excitation in the S1 state leads to an might be still desirable in order to increase the efficiency of
increase of π-conjugation between thiophene and phenyl frag- newly synthesized dyes.
ments of these molecules. As a result, molecular structures of
3a–c in the first singlet excited state are significantly flattened Photovoltaic Performance of the DSSC
compared to the ground state structures (Fig. S9 in
Supplementary Material). These structural changes appear to Compound 3b has been used as a photosensitizer for perfor-
cause the observed Stokes shifts. mance in trial DSSC because this dye has a maximum extinc-
Correct prediction of emission, as well as vertical excita- tion coefficient in the solutions among studied dyes (see
tion spectra, requires consideration of the excited state elec- Table 1). Fig. 11 shows I – V characteristic of DSSC, fabricat-
tronic density and the solvent reaction field in self-consistent ed on TiO2 photoanodes with adsorbed 3b dye upon illumi-
manner. It is particularly important for a long range electron nation (100 mW×cm−2). We used acetonitrile solution in the
transfer processes, when variations of the dipole moments presence of 0.5 M LiI+0.05 M I2 as a redox – system. The
associated with electronic transitions are significant. For this short circuit current density (Isc) was 2.04 mA cm−2, and the
reason, a more accurate and physically meaningful state- open circuit voltage (Uoc) was 0.525 V. The calculated power
specific approach [38] has been used in a PCM TDDFT cal- conversion efficiency of a cell (η) was 0.91 at a fill factor (FF)
culation, instead of standard linear response [51] method. of 0.85.

Fig. 10 The frontier molecular orbitals of 3a–c involved in the S0-S1 transitions as calculated by the PCM-CAM-B3LYP/6-311+G (d,p) method
(0.03 a.u. contour threshold has been used)
J Fluoresc

Table 4 Calculated emission energy E*calc (eV) and oscillator strength f of the S1-S0 transitions of 3a–c according to the TD PCM-CAM-B3LYP/6-
311+G(d,p) calculation in toluene, dichloromethane and DMSO solutions. E*exp (eV) correspond to the observed emission maxima

Dye Toluene Dichloromethane DMSO

E*calc, eV f E*exp, eV E*calc, eV f E*exp, eV E*calc, eV f E*exp, eV

3a 2.856 1.2112 2.890 2.600 1.2176 2.627 2.471 1.2155 2.490

3b 2.875 1.6133 2.938 2.734 1.6101 2.684 2.668 1.6106 2.480
3c 2.570 1.5273 2.546 2.460 1.5459 2.510 2.411 1.5553 2.422

In our opinion, low overall efficiency of DSSG is due the sensitizers in DSSC devices have shown to exhibit the con-
following reason. The absorption maximum of 3b dye appears version efficiency of 0.91 %, the fill factor (FF) of 85 %, the
at the region 350–410 nm (see Fig. S2), and such position of short-circuit photocurrent density (Isc) of 2.04 mA cm−2, the
the absorption band does not correspond to the maximum of open-circuit voltage (Uoc) of 0.525 V for example of dye 3b.
the solar radiation spectrum. Despite the fact that the described photovoltaic device showed
relatively low efficiency coefficients, our studies open ave-
nues for the development of organic dyes featuring azine as
Conclusion a new anchoring group. By appropriate structural modifica-
tions, electron-withdrawing pyrimidine can be developed,
Three novel 9-phenyl-9H-carbazole-π-pyrimidine dyes have which may serve as an efficient anchoring group.
been obtained through combination of the microwave-
mediated Suzuki cross-coupling reaction and nucleophilic ar- Acknowledgments This work was supported by the Russian Founda-
omatic substitution of hydrogen (SNH). tion for Basic Research (research projects No. 13-03-96049-r_ural_a, 13-
03-12434 ofi_м2, 13-03-90606-Arm_a, 14-03-01017-А, 14-03-00479-А
All dyes exhibit a strong fluorescence with high quantum and 14-03-31040-mol_а, 13-03-12415), the Council on Grants at the
yields, and they demonstrate solvatochromic properties, thus President of the Russian Federation (Program of State Support for Lead-
allowing one to use these compounds as polarity sensors. ing Scientific Schools of the Russian Federation and Young Scientists,
Besides that, the scope of spectral, computational and electro- Grant MK-3939.2014.3). N.I. Makarova, I.V. Dorogan, A.V. Metelitsa
and V.I. Minkin would like to acknowledge the financial support of ab-
chemical studies suggests that these dyes appear to be good sorption, fluorescence and quantum chemical studies from the Ministry of
photosensitizers in DSSC. Their LUMOs lay over the conduc- Education and Science of Russian Federation in the framework of the
tion band edge of TiO2, while their HOMOs are under the State Assignment for Research project № 1895.
reduction potential energy of the electrolytes (I−/I3−), thus cor-
responding to the ability of electron transfer from the dye
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