See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/281148600

Dyes and Pigments

Article in Dyes and Pigments · August 2015

DOI: 10.1016/j.dyepig.2015.07.034

CITATIONS READS

12 155

4 authors, including:

Justin Thomas K R Chuan-Pei Lee

Indian Institute of Technology Roorkee University of California, Berkeley
192 PUBLICATIONS 5,774 CITATIONS 102 PUBLICATIONS 2,179 CITATIONS

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Advanced Energy Materials & Devices View project

Concise Molecules with Precise Properties View project

All content following this page was uploaded by Chuan-Pei Lee on 23 October 2017.

The user has requested enhancement of the downloaded file.

 Dyes and Pigments 123 (2015) 154e165

Contents lists available at ScienceDirect

Dyes and Pigments

journal homepage: www.elsevier.com/locate/dyepig

Organic dyes containing fluoreneamine donor and carbazole p-linker

for dye-sensitized solar cells
K.R. Justin Thomas a, *, A. Venkateswararao a, Chuan-Pei Lee b, Kuo-Chuan Ho b
a
Organic Materials Laboratory, Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, 247 667, India
b
Department of Chemical Engineering, National Taiwan University, Taipei, 10617, Taiwan

a r t i c l e i n f o a b s t r a c t

Article history: A series of new organic dyes containing fluoreneamine-based donor and carbazole p-spacer are reported.
Received 8 May 2015 These dyes displayed longer wavelength charge transfer absorption when compared to that of the cor-
Received in revised form responding phenylamine analogs. Fluoreneamine-based donors shifted the lowest unoccupied molecular
18 July 2015
orbital upwardly which is beneficial for the injection of electrons from the excited dye into the con-
Accepted 25 July 2015
Available online 1 August 2015
duction band of TiO2 and lowered the oxidation potential of the dyes. The electronic perturbations
caused by the fluorene unit have been confirmed by the density functional theoretical calculations. A
device fabricated using a dye featuring difluorenylaminocarbazole donor and thiophene in the p-spacer
Keywords:
Carbazole
exhibited promising power conversion efficiency (6.4%). The interfacial electron transfer kinetics has
Fluorene been elucidated by electrochemical impedance spectroscopy which showed the beneficial role of
Arylamine difluorenylamine unit in suppressing the electron recombination.
Light-harvesting © 2015 Elsevier Ltd. All rights reserved.
Dye-sensitized solar cells
TDDFT computations

1. Introduction additional donor (D1-p-D2-p-A) or acceptor (A2-p-D-p-A1) [7bef].

Organic dyes have been intensively developed in the recent
years for application as emitters in organic light-emitting diodes,
electron donors in bulk heterojunction solar cells or perovskite
solar cells and sensitizers in dye-sensitized solar cells (DSSCs)
[1e4]. Organic dyes have also been utilized as semiconductors in
thin-film transistors and developed as chromophores possessing
unusual non-linear optical properties such as polarizability and
two-photon absorption [5,6]. In order for a dye to function as
sensitizer in DSSCs, it should possess excellent visible region ab-
sorption and facile photo-induced intramolecular charge transfer
[4]. Several molecular configurations such as DepeA, D1-p-D2-p-A,
A1-p-D-p-A1, DepeA1-p-A2 and A2-p-D-p-A1 featuring different
electron donors (D) and electron acceptors (A) have been found to
fulfill the above requirements [7]. For efficient functioning in
DSSCs, besides possessing light harvesting capability, the sensi-
tizers also need to inherit special qualities to retard the detrimental
processes such as electron recombination and dye-aggregation [4].
Electronic property manipulations were demonstrated for the
simple donor-acceptor dyes (DepeA) by the introduction of
* Corresponding author. Tel.: þ91 1332 285376.
E-mail address: krjt8fcy@iitr.ac.in (K.R. Justin Thomas).
Similarly, for the dianchoring dyes, several chromophoric config-
urations such as rigid rod (A-p-D-p-A), Y-shape (D-(p-A)2) and H-
shape ((DepeA)2) have been used and their benefits evaluated [8].
In a simple DepeA configuration, nature of donor and linker seg-
ments can be changed to fine-tune the electronic energies or steric
requirements [4].
Triarylamine donors are most attractive due to their promising
photo- and redox stability [4b]. Triarylamine-based organic dyes
containing polyaromatic/heteroaromatic chromophores such as
fluorene [9], phenothiazine [10], phenoxazine [11], indoline [12],
coumarin [13], cyclopentadithiophene [14], dithienothiophene
[15], dithienopyrrole [16], etc. have been developed and found to
function as effective sensitizers. Most of the units mentioned above
are electron-rich in nature and enhance the charge transfer char-
acteristics by increasing the donor strength of the molecule
[10e16]. Also, these electron-releasing groups stabilize the
oxidized dye generated due to the electron injection from the dye
into the conduction band of TiO2. Additionally, bulkiness of the
polyaromatic chromophore combined with its hydrophobicity is
helpful to hinder the close association of the dyes on the surface of
TiO2 and to forbid the approach of polar electrolyte components at
the surface of TiO2 [17]. In this regard, a classic example was pro-
vided by Chow and co-workers [18]. They found that replacement

http://dx.doi.org/10.1016/j.dyepig.2015.07.034
0143-7208/© 2015 Elsevier Ltd. All rights reserved.
 K.R. Justin Thomas et al. / Dyes and Pigments 123 (2015) 154e165
of diphenylamine unit by naphthylphenylamine in a dye led to
significant increase in open circuit voltage (VOC). This is attributed
to the effectiveness of naphthylphenylamine in hindering the self-
aggregation of the dyes on TiO2 surface and facile stabilization of
the oxidized dye. Thus, the organic dyes containing chromophores
featuring sufficient steric bulk and extended conjugation are useful.
Organic dyes containing difluorenylamine donor have been
extensively studied. Ko and co-workers for the first time introduced
difluorenylamine donor in organic dyes and achieved high power
conversion efficiency above 8% [9b]. Gr€ atzel and co-workers further
developed dyes based on thieno[3,2-b]thiophene linker and
difluorenylamine donor and found to possess high molar extinction
coefficients for the charge transfer transition [19]. Ko and co-
workers reported dyes based on p-phenylenevinylene linker and
difluorenylamine donor [20]. Organic dyes showing panchromatic
absorption and featuring electron-deficient chromophores such as
benzo[1,2,5]thiadiazole or squaraine and difluorenylamine donor
were also reported [21]. Thomas and co-workers synthesized
fluorene-based dyes which showed longer wavelength absorption
when compared to dyes containing phenylene linker [22]. The su-
perior efficiency of the fluorene-based dyes is attributed to the
difluorenylamine unit which offers strong donating strength, bulky
structure which suppresses the aggregation and keeps away the
electrolyte from TiO2 film. The beneficial properties of difluor-
enylamine unit are due to the following reasons: (1) bulky trigonal
structure with rigidity and extended conjugation and (2) the
presence of alkyl chains at C9-position. Also, it has been found that
light harvesting potential of the dyes containing difluorenylamine
donor is largely dependent on the nature of linker which crucially
alters the donor-acceptor interactions.
In our earlier report, we successfully demonstrated 2,7-di-
substituted carbazole-based sensitizers with promising power
conversion efficiencies [23]. We felt that the introduction of
difluorenylamine donor in the above design may be beneficial to
increment the absorption properties and inhibit the detrimental
processes such as electron recombination and molecular aggrega-
tion. To test this hypothesis, we have designed and synthesized new
organic dyes featuring fluorenylphenylamine and difluorenylamine
donors connected to the cyanoacrylic acid acceptor via 2,7-
carbazole linker (Fig. 1). We studied the effect of fluorene present
in the donor segment on the optical, electrochemical and photo-
voltaic properties. Introduction of fluorene in the donor moiety
red-shifted the charge transfer absorption and imparted redox
stability to the dyes. Also suppression of back electron transfer was
identified by electrochemical impedance spectroscopy studies
attributable to the presence of fluorene unit.
2. Experimental section
2.1. Materials and methods
The precursor chemicals were purchased from commercial
sources and used as received. Solvents used in reactions and
Fig. 1. Structures of the carbazole based dyes.
155
spectroscopy measurements were dried by following standard
distillation methods. Column chromatography purifications were
performed on silica gel (230e400 mesh) packed in a column
measuring 40 cm long and 3.0 cm diameter. The IR spectra were
recorded with a NEXUS FT-IR spectrometer (Thermonicolet) by
using KBr pellets. The 1H and 13C NMR spectra were recorded on a
Bruker Avance 3 spectrometer operating at 500.13 and 125.77 MHz
respectively. Deuterated chloroform (CDCl3) and dimethyl sulfoxide
(DMSO-d6) were used as solvent and the residual peaks at d 7.26
and 2.52 for 1H; 77.0 and 39.5 for 13C, were used to calibrate the
chemical shifts. Absorption and emission spectra were measured in
spectroscopic grade solvents at room temperature in quartz cu-
vettes using a Cary 100 spectrophotometer and Shimadzu RF5301
spectrofluorimeter respectively. The cyclic voltammetry (CV) and
differential pulse voltammetry (DPV) measurements were per-
formed using BASi Epsilon electrochemical analyzer. A standard
three-electrode assembly containing glassy carbon working elec-
trode, a non-aqueous Ag/AgNO3 reference electrode and a platinum
auxiliary working electrode was used. The experiments were per-
formed at room temperature under nitrogen atmosphere in
dichloromethane with Bu4NClO4 (0.1 M) as supporting electrolyte.
The high resolution mass spectra were obtained from a Bruker
micrOTOF-QII ESI mass spectrometer in the positive ion mode.
2.2. Synthesis
The precursors, 2,7-dibromo-9-butyl-9H-carbazole [24] (1), 2-
bromo-9,9-diethyl-9H-fluorene [25] and 9,9-diethyl-9H-fluoren-
2-amine [26] were synthesized by following the reported
procedures.
2.2.1. N-phenyl-9,9-dipropyl-9H-fluoren-2-amine (2a)
A mixture of 2-bromo-9,9-diethyl-9H-fluorene (3.29 g,
10 mmol), aniline (1.12 g, 12 mmol), Pd(dba)2 (0.05 g, 0.20 mmol),
dppf (0.06 g, 0.20 mmol), sodium tert-butoxide (2.40 g, 25 mmol),
and toluene (25 mL) was taken in a pressure tube and heated at
80  C for 48 h under N2 atmosphere. After completion of the re-
action, the volatiles were removed under vacuum, and the resulting
solution extracted with dichloromethane (3  60 mL). The com-
bined organic extract was washed with brine solution, dried over
Na2SO4, and concentrated to leave a yellow solid. Further, the crude
product was purified by column chromatography on silica gel by
using hexane/dichloromethane mixture (2:1 v/v) as an eluant.
White powder; Yield 2.37 g (70%); mp 77e79  C; 1H NMR (CDCl3,
500.13 MHz) d 7.57e7.61 (m, 2H), 7.27e7.31 (m, 4H), 7.21e7.24 (m,
1H), 7.06e7.10 (m, 3H), 7.05 (dd, J ¼ 7.5 Hz, J ¼ 2.0 Hz, 1H),
6.91e6.95 (m, 1H), 5.82 (s, 1H), 1.86e1.93 (m, 4H), 0.64e0.73 (m,
10H); 13C NMR (CDCl3, 125.77 MHz) d 152.5, 150.3, 143.7, 142.3,
141.3, 134.9, 129.5, 126.8, 126.0, 122.8, 120.7, 120.5, 118.9, 117.4, 117.2,
116.9, 113.1, 52.3, 43.0, 17.3, 14.6; HRMS calcd for C25H27N [M]þ m/z
341.2138, found 341.2123.
2.2.2. Bis(9,9-diethyl-9H-fluoren-2-yl)amine (2b)
It was prepared from 2-bromo-9,9-diethyl-9H-fluorene (3.01 g,
10 mmol) and 9,9-diethyl-9H-fluoren-2-amine (2.84 g, 12 mmol) by
following a procedure described above for 2a. White powder; Yield
2.92 g (64%); mp 160e162  C; 1H NMR (DMSO-d6, 500.13 MHz)
d 8.45 (s, 1H), 7.40 (d, J ¼ 8.0 Hz, 4H), 7.05e7.09 (m, 4H), 6.98e7.01
(m, 2H), 6.96 (d, J ¼ 1.5 Hz, 2H), 6.85 (dd, J ¼ 7.5 Hz, J ¼ 2.0 Hz, 2H),
1.73e1.84 (m, 8H), 0.13 (t, J ¼ 2.0 Hz, 12H); 13C NMR (DMSO-d6,
125.77 MHz) d 150.5, 148.6, 143.1, 141.3, 133.2, 126.8, 125.6, 122.6,
120.7, 118.6, 116.2, 111.1, 55.3, 32.0, 8.5; HRMS calcd for C34H35N
[M]þ m/z 457.2764, found 457.2745.
156 K.R. Justin Thomas et al. / Dyes and Pigments 123 (2015) 154e165
2.2.3. 7-Bromo-9-butyl-N-(9,9-dipropyl-9H-fluoren-2-yl)-N-
phenyl-9H-carbazol-2-amine (3a)
A mixture of 2,7-dibromo-9-butyl-9H-carbazole (1, 3.81 g,
10 mmol), 2a (1.70 g, 5 mmol), Pd(dba)2 (0.03 g, 0.10 mmol), dppf
(0.03 g, 0.10 mmol), sodium tert-butoxide (1.40 g, 12.5 mmol), and
toluene (10 mL) was charged in a pressure tube and heated at 80  C
for 48 h under N2 atmosphere. After completion of the reaction, the
volatiles were removed under vacuum, and the resulting solution
was extracted with dichloromethane (3  60 mL). The combined
organic extract was washed with brine solution, dried over Na2SO4,
and concentrated. Further, the crude product was purified by col-
umn chromatography on silica gel by using hexane/dichloro-
methane mixture (5:2 v/v) as an eluant. White solid; Yield 1.92 g
(60%); mp 144e146  C; 1H NMR (CDCl3, 500.13 MHz) d 7.88 (d,
J ¼ 8.5 Hz, 1H), 7.83 (d, J ¼ 8.0 Hz, 1H), 7.61 (d, J ¼ 7.5 Hz, 1H), 7.57 (d,
J ¼ 8.0 Hz, 1H), 7.46 (d, J ¼ 0.5 Hz, 1H), 7.28e7.31 (m, 4H), 7.24 (s,
2H), 7.18 (s, 3H), 7.02e7.10 (m, 4H), 4.06 (t, J ¼ 7.5 Hz, 2H), 1.78e1.91
(m, 4H), 1.68e1.75 (quintet, J ¼ 7.5 Hz, 2H), 1.25e1.32 (m, 2H),
0.85e0.88 (m, 3H), 0.70e0.75 (m, 10H); 13C NMR (CDCl3,
125.77 MHz) d 152.1, 150.6, 148.4, 147.4, 146.9, 141.8, 141.7, 140.9,
136.3, 129.2, 126.8, 126.3, 123.7, 123.6, 122.8, 122.4, 122.1, 120.8,
120.3, 119.3, 119.1, 118.3, 117.8, 117.0, 111.6, 104.4, 55.3, 42.8, 42.6,
30.9, 20.5, 17.3, 14.6, 13.8; HRMS calcd for C41H41BrN2 [M]þ m/z
640.2448, found 640.2456.
2.2.4. 7-Bromo-9-butyl-N,N-bis(9,9-diethyl-9H-fluoren-2-yl)-9H-
carbazol-2-amine (3b)
It was prepared from 1 (3.81 g, 10 mmol) and 2b (1.81 g, 5 mmol)
by following a procedure described above for 3a. White solid; Yield
2.37 g (48%); mp 158e160  C; 1H NMR (CDCl3, 500.13 MHz)
d 7.82e7.93 (m, 2H), 7.58e7.66 (m, 4H), 7.47 (d, J ¼ 10.0 Hz, 1H),
7.24e7.32 (m, 7H), 7.22 (d, J ¼ 9.0 Hz, 2H), 7.12 (d, J ¼ 5.0 Hz, 2H),
7.05e7.09 (m, 2H), 4.04 (t, J ¼ 7.0 Hz, 2H), 1.85e1.97 (m, 8H), 1.71 (t,
J ¼ 7.0 Hz, 2H), 1.25e1.30 (m, 2H), 0.83e0.88 (m, 3H), 0.37 (t,
J ¼ 7.0 Hz, 12H); 13C NMR (CDCl3, 125.77 MHz) d 151.3, 149.7, 147.7,
147.2, 141.8, 141.4, 136.6, 126.9, 126.3, 123.3, 122.8, 122.0, 120.84,
120.77, 120.3, 119.1, 118.9, 118.3, 117.7, 116.9, 111.6, 104.1, 56.1, 42.9,
32.8, 30.9, 20.5, 13.8, 8.6; HRMS calcd for C50H49BrN2Na [M þ Na]þ
m/z 779.2971, found 779.2971.
2.2.5. 5-(9-Butyl-7-((9,9-dipropyl-9H-fluoren-2-yl) (phenyl)
amino)-9H-carbazol-2-yl)thiophene-2-carbaldehyde (4a)
A mixture of 3a (0.64 g, 1 mmol) and (5-(1,3-dioxolan-2-yl)
thiophen-2-yl)tributylstannane (0.49 g, 1.1 mmol) in dry DMF
(5 mL) was kept under nitrogen atmosphere. The catalyst,
Pd(PPh3)2Cl2 (0.01 g, 0.01 mmol) was added. The reaction was
heated at 80  C for 16 h. After cooling the reaction mixture, it was
poured into water. The organic compound was extracted with
dichloromethane (3  50 mL). The combined organic extract was
washed with brine solution, dried over Na2SO4, and concentrated to
leave a yellow solid. This crude product was dissolved in 5 mL of
acetic acid and heated at 65  C for 2 h. After that 5 mL of water was
added and continued heating for further 2 h. After cooling to room
temperature, the reaction mixture was extracted with dichloro-
methane and dried over anhydrous Na2SO4. Finally, the crude
product was purified by column chromatography on silica gel by
using hexane/dichloromethane mixture (1:1 v/v) as an eluant:
Yellow solid; Yield 0.52 g (77%); mp 141e143  C; IR (KBr, cm1)
1663 (nC]O); 1H NMR (CDCl3, 500.13 MHz) d 9.90 (s, 1H), 8.01 (d,
J ¼ 8.0 Hz, 1H), 7.92 (d, J ¼ 8.5 Hz, 1H), 7.77 (d, J ¼ 4.0 Hz, 1H), 7.62
(d, J ¼ 8.0 Hz, 1H), 7.59 (d, J ¼ 5.0 Hz, 1H), 7.58 (s, 2H), 7.54 (dd,
J ¼ 8.0 Hz, J ¼ 1.5 Hz, 1H), 7.50 (d, J ¼ 4.0 Hz, 1H), 7.30e7.31 (m, 3H),
7.28 (s, 1H), 7.19e7.20 (m, 3H), 7.08e7.11 (m, 2H), 7.02e7.04 (m, 2H),
4.45 (t, J ¼ 7.0 Hz, 2H), 1.83e1.89 (m, 2H), 1.76e1.78 (m, 4H),
1.31e1.33 (m, 2H), 0.89 (t, J ¼ 2.5 Hz, 3H), 0.68e0.76 (m, 10H); 13C
NMR (CDCl3, 125.77 MHz) d 182.8, 156.1, 152.2, 150.6, 148.3, 147.33,
147.31, 142.6, 141.8, 141.1, 140.9, 137.7, 136.5, 129.5, 129.2, 126.8,
126.4, 124.2, 123.9, 123.7, 122.8, 122.6, 121.1, 120.4, 120.2, 119.5,
119.2, 117.82, 117.75, 116.9, 106.4, 104.0, 55.3, 42.7, 42.6, 31.1, 20.5,
17.4, 14.6, 13.9; HRMS calcd for C46H44N2OSNa [M þ Na]þ m/z
695.3067, found 695.3062.
2.2.6. 5-(7-(Bis(9,9-diethyl-9H-fluoren-2-yl)amino)-9-butyl-9H-
carbazol-2-yl)thiophene-2-carbaldehyde (4b)
Compound 4b was synthesized from 3b (0.76 g, 1 mmol) and (5-
(1,3-dioxolan-2-yl)thiophen-2-yl)tributylstannane (0.49 g,
1.1 mmol) mixture by following a procedure similar to that
described above for 4a. Yellow solid; Yield 0.42 g (70%); mp
104e106  C; IR (KBr, cm1) 1662 (nC]O); 1H NMR (CDCl3,
500.13 MHz) d 9.90 (s, 1H), 8.00 (d, J ¼ 8.0 Hz, 1H), 7.93 (d, J ¼ 8.5 Hz,
1H), 7.77 (d, J ¼ 4.5 Hz, 1H), 7.65 (d, J ¼ 7.0 Hz, 2H), 7.60e7.61 (m,
3H), 7.54 (dd, J ¼ 8.0 Hz, J ¼ 2.0 Hz, 1H), 7.49 (d, J ¼ 3.5 Hz, 1H),
7.25e7.34 (m, 6H), 7.21 (d, J ¼ 5.0 Hz, 2H), 7.13e7.15 (m, 3H), 7.07
(dd, J ¼ 7.5 Hz, J ¼ 2.0 Hz, 1H), 4.13 (t, J ¼ 7.0 Hz, 2H), 1.94e2.00 (m,
4H), 1.86e1.92 (m, 4H), 1.74e1.77 (m, 2H), 1.28e1.33 (m, 3H), 0.38 (t,
J ¼ 7.5 Hz, 12H); 13C NMR (CDCl3, 125.77 MHz) d 182.7, 156.1, 151.3,
149.7, 147.61, 147.58, 142.6, 141.8, 141.4, 141.1, 137.7, 136.7, 129.4,
126.9, 126.4, 124.2, 123.7, 123.4, 122.8, 121.1, 120.3, 120.2, 119.1, 119.0,
117.8, 117.6, 116.8, 106.4, 103.7, 56.1, 42.8, 32.8, 31.0, 20.5, 13.8, 8.6;
HRMS calcd for C55H52N2OSNa [M þ Na]þ m/z 811.3693, found
811.3677.
2.2.7. 5-(5-(9-Butyl-7-((9,9-dipropyl-9H-fluoren-2-yl) (phenyl)
amino)-9H-carbazol-2-yl)thiophen-2-yl)thiophene-2-carbaldehyde
(5a)
Compound 5a was obtained from 3a (0.64 g, 1 mmol) and (5-
(5-(1,3-dioxolan-2-yl)thiophen-2-yl)thiophen-2-yl)tributyl-
stannane (0.58 g, 1.1 mmol) mixture by following a procedure
similar to that described above for 4a. Orange solid; Yield 0.70 g
(93%); mp 129e131  C; IR (KBr, cm1) 1661 (nC]O); 1H NMR
(CDCl3, 500.13 MHz) d 9.87 (s, 1H), 7.99 (d, J ¼ 8.0 Hz, 1H), 7.92 (d,
J ¼ 8.5 Hz, 1H), 7.69 (d, J ¼ 8.0 Hz, 1H), 7.62e7.63 (m, 1H), 7.58 (d,
J ¼ 8.0 Hz, 1H), 7.53 (d, J ¼ 1.0 Hz, 1H), 7.48 (dd, J ¼ 8.0 Hz,
J ¼ 1.5 Hz, 1H), 7.37 (dd, J ¼ 11.5 Hz, J ¼ 4.0 Hz, 2H), 7.28e7.32 (m,
5H), 7.19e7.20 (m, 3H), 7.08e7.12 (m, 2H), 7.02e7.03 (m, 2H), 4.16
(t, J ¼ 7.5 Hz, 2H), 1.75e1.92 (m, 6H), 1.31e1.35 (m, 2H), 0.89 (t,
J ¼ 7.5 Hz, 3H), 0.67e0.68 (m, 10H); 13C NMR (CDCl3, 125.77 MHz)
d 182.4, 152.1, 150.6, 148.4, 147.8, 147.4, 147.0, 142.4, 141.4, 141.2,
140.9, 137.5, 136.4, 134.5, 130.1, 129.2, 127.3, 126.8, 126.3, 123.9,
123.81, 123.77, 123.6, 123.3, 122.8, 122.5, 120.9, 120.3, 120.2, 119.4,
119.1, 118.0, 117.5, 116.9, 105.7, 104.2, 55.3, 42.6, 31.1, 26.9, 20.5, 17.3,
14.6, 13.9; HRMS calcd for C50H46N2OS2Na [M þ Na]þ m/z
777.2944, found 777.2952.
2.2.8. 5-(5-(7-(Bis(9,9-diethyl-9H-fluoren-2-yl)amino)-9-butyl-
9H-carbazol-2-yl)thiophen-2-yl)thiophene-2-carbaldehyde (5b)
Compound 5b was synthesized from 3b (0.76 g, 1.1 mmol) and
(5-(5-(1,3-dioxolan-2-yl)thiophen-2-yl)thiophen-2-yl)tributyl-
stannane (0.58 g, 1.1 mmol) mixture by following a procedure
similar to that described above for 4a. Orange solid; Yield 0.62 g
(71%); mp 165e167  C; IR (KBr, cm1) 1656 (nC]O); 1H NMR (CDCl3,
500.13 MHz) d 9.87 (s, 1H), 7.99 (d, J ¼ 8.0 Hz, 1H), 7.92 (d, J ¼ 8.5 Hz,
1H), 7.69 (d, J ¼ 11.5 Hz, 1H), 7.64 (d, J ¼ 7.5 Hz, 2H), 7.60 (d,
J ¼ 8.0 Hz, 2H), 7.53 (s, 1H), 7.48 (dd, J ¼ 8.0 Hz, J ¼ 1.0 Hz, 1H), 7.36
(dd, J ¼ 10.0 Hz, J ¼ 4.0 Hz, 2H), 7.27e7.33 (m, 7H), 7.21 (d,
J ¼ 2.0 Hz, 2H), 7.13e7.15 (m, 3H), 7.06 (dd, J ¼ 8.5 Hz, J ¼ 1.5 Hz, 1H),
4.14 (t, J ¼ 7.0 Hz, 2H), 1.94e1.99 (m, 2H), 1.87e1.91 (m, 2H),
1.75e1.78 (m, 2H), 1.30e1.34 (m, 2H), 0.87 (t, J ¼ 7.5 Hz, 3H), 0.38 (t,
J ¼ 7.5 Hz, 12H); 13C NMR (CDCl3, 125.77 MHz) d 182.4, 151.3, 149.7,
147.9, 147.7, 147.5, 147.2, 142.4, 141.40, 141.36, 141.2, 137.5, 136.6,
 K.R. Justin Thomas et al. / Dyes and Pigments 123 (2015) 154e165
134.5, 130.0, 127.3, 126.9, 126.3, 123.9, 123.8, 123.3, 122.8, 120.9,
120.3, 120.1, 119.1, 118.9, 117.9, 117.5, 116.8, 105.7, 103.9, 56.1, 42.7,
32.8, 31.1, 20.5, 13.8, 8.6; HRMS calcd for C59H54N2OS2 [M]þ m/z
870.3672, found 870.3658.
2.2.9. (E)-3-(5-(9-Butyl-7-((9,9-dipropyl-9H-fluoren-2-yl) (phenyl)
amino)-9H-carbazol-2-yl)thiophen-2-yl)-2-cyanoacrylic acid (6a)
The aldehyde 4a (0.22 g, 0.33 mmol), 2-cyanoacetic acid (0.04 g,
0.5 mmol), ammonium acetate (0.04 g, 0.25 mmol), and acetic acid
(5 mL) were mixed and refluxed for 24 h. The resulting red pre-
cipitate was filtered and washed several times with water and
dried. It was crystallized from dichloromethane/hexane mixture to
obtain the analytically pure sample. Red solid; Yield 0.23 g (94%);
mp 216e218  C; IR (KBr, cm1) 2217 (nC≡N); 1H NMR (CDCl3,
500.13 MHz) d 8.37 (s, 1H), 8.02 (d, J ¼ 8.0 Hz, 1H), 7.92 (d, J ¼ 8.5 Hz,
1H), 7.82 (d, J ¼ 4.0 Hz, 1H), 7.62 (d, J ¼ 9.0 Hz, 2H), 7.56e7.60 (m,
2H), 7.54 (d, J ¼ 4.0 Hz, 1H), 7.32-7.30 (m, 3H), 7.28 (s, 1H), 7.27 (s,
1H), 7.20e7.21 (m, 3H), 7.08e7.10 (m, 2H), 7.05e7.07 (m, 2H), 4.17 (t,
J ¼ 7.5 Hz, 2H), 1.74e1.91 (m, 4H), 1.29e1.34 (m, 2H), 0.88 (t,
J ¼ 7.0 Hz, 4H), 0.68e0.70 (m, 10H); 13C NMR (CDCl3, 125.77 MHz)
d 152.2, 150.6, 148.2, 147.5, 147.2, 142.7, 140.9, 136.5, 134.2, 129.2,
129.0, 126.8, 126.4, 124.3, 124.0, 123.8, 122.8, 122.7, 121.2, 120.4,
119.5, 119.2, 118.0, 117.6, 106.4, 103.9, 55.3, 42.6, 31.1, 20.4, 17.3, 14.6,
13.9; HRMS calcd for C49H45N3O2S [M]þ m/z 739.3227, found
739.3223.
2.2.10. (E)-3-(5-(7-(Bis(9,9-diethyl-9H-fluoren-2-yl)amino)-9-
butyl-9H-carbazol-2-yl)thiophen-2-yl)-2-cyanoacrylic acid (6b)
Compound 6b was obtained from 4b (0.39 g, 0.5 mmol) by
following a procedure similar to that described above for 6a. Dark
red solid; Yield 0.41 g (95%); mp 224e226  C; IR (KBr, cm1) 2208
(nC≡N); 1H NMR (CDCl3, 500.13 MHz) d 8.36 (s, 1H), 8.02 (d,
J ¼ 8.0 Hz, 1H), 7.93 (d, J ¼ 8.0 Hz, 1H), 7.82 (d, J ¼ 4.5 Hz, 1H), 7.65
(d, J ¼ 7.5 Hz, 2H), 7.61 (d, J ¼ 8.0 Hz, 3H), 7.56e7.58 (m, 1H), 7.54 (d,
J ¼ 4.0 Hz, 1H), 7.28e7.34 (m, 6H), 7.22 (d, J ¼ 2.5 Hz, 2H), 7.12e7.15
(m, 3H), 7.07e7.09 (m, 1H), 4.16 (t, J ¼ 6.5 Hz, 2H), 1.96e2.00 (m,
4H), 1.86e1.91 (m, 4H), 1.75 (q, J ¼ 7.5 Hz, 2H), 1.28e1.33 (m, 2H),
0.86 (t, J ¼ 7.5 Hz, 3H), 0.38 (t, J ¼ 7.5 Hz, 12H); 13C NMR (CDCl3,
125.77 MHz) d 158.2, 151.3, 149.7, 148.0, 147.8, 147.5, 142.8, 141.4,
141.1, 140.5, 136.8, 134.2, 128.9, 126.9, 124.7, 124.3, 123.5, 122.8,
120.33, 120.25, 119.1, 118.1, 117.5, 116.8, 115.9, 106.4, 103.6, 56.1, 42.7,
32.8, 31.1, 20.4, 13.8, 8.6; HRMS calcd for C58H53N3O2SNa [M þ Na]þ
m/z 878.3751, found 878.3748.
2.2.11. (E)-3-(5-(5-(9-Butyl-7-((9,9-dipropyl-9H-fluoren-2-yl)
(phenyl)amino)-9H-carbazol-2-yl)thiophen-2-yl)thiophen-2-yl)-2-
cyanoacrylic acid (7a)
It was obtained from 5a (0.38 g, 0.5 mmol) by following a pro-
cedure similar to that described above for 6a. Violet solid; Yield
0.38 g (93%); mp 257e259  C; IR (KBr, cm1) 2213 (nC≡N); 1H NMR
(CDCl3, 500.13 MHz) d 8.32 (s, 1H), 8.00 (d, J ¼ 3.0 Hz, 1H), 7.91 (d,
J ¼ 8.5 Hz, 1H), 7.72 (d, J ¼ 4.0 Hz, 1H), 7.62e7.63 (m, 1H), 7.58 (d,
J ¼ 8.5 Hz, 1H), 7.54 (s, 1H), 7.48 (dd, J ¼ 8.0 Hz, J ¼ 1.5 Hz, 1H), 7.45
(d, J ¼ 4.0 Hz, 1H), 7.39 (d, J ¼ 4.0 Hz, 1H), 7.28e7.33 (m, 5H), 7.25 (s,
1H), 7.19e7.20 (m, 3H), 7.11 (d, J ¼ 2.0 Hz, 1H), 7.09 (dd, J ¼ 8.0 Hz,
J ¼ 2.0 Hz, 1H), 7.01e7.05 (m, 2H), 4.16 (t, J ¼ 7.5 Hz, 2H), 1.77e1.89
(m, 6H), 1.33e1.34 (m, 2H), 0.88e0.91 (t, J ¼ 7.0 Hz, 3H),
0.667e0.673 (m, 10H); 13C NMR (CDCl3, 125.77 MHz) d 152.1, 150.6,
148.4, 147.8, 147.5, 147.4, 147.0, 142.4, 141.3, 141.2, 140.9, 137.6, 136.3,
134.5, 130.1, 129.2, 127.3, 126.8, 126.3, 123.9, 123.83, 123.77, 123.6,
123.2, 122.8, 122.5, 120.9, 120.3, 120.2, 119.3, 119.1, 118.0, 117.5, 116.9,
105.7, 104.2, 55.3, 42.6, 31.1, 26.9, 20.5, 17.6, 17.3, 14.6, 13.9; HRMS
calcd for C53H47N3O2S2 [M]þ m/z 821.3104, found 821.3103.
157
2.2.12. (E)-3-(5-(5-(7-(Bis(9,9-diethyl-9H-fluoren-2-yl)amino)-9-
butyl-9H-carbazol-2-yl)thiophen-2-yl)thiophen-2-yl)-2-
cyanoacrylic acid (7b)
It was obtained from 5b (0.44 g, 0.5 mmol) by following a pro-
cedure similar to that described above for 6a. Violet solid; Yield
0.43 g (92%); mp 230e232  C; IR (KBr, cm1) 2215 (nC≡N); 1H NMR
(CDCl3, 500.13 MHz) d 8.31 (s, 1H), 8.00 (d, J ¼ 8.0 Hz, 1H), 7.92 (d,
J ¼ 8.5 Hz, 1H), 7.72 (d, J ¼ 4.0 Hz, 1H), 7.64 (d, J ¼ 7.5 Hz, 2H), 7.60 (d,
J ¼ 8.0 Hz, 2H), 7.54 (s, 1H), 7.49 (d, J ¼ 8.0 Hz, 1H), 7.45 (d, J ¼ 3.5 Hz,
1H), 7.39 (d, J ¼ 4.0 Hz, 1H), 7.28e7.34 (m, 6H), 7.25 (s, 1H), 7.21 (d,
J ¼ 3.5 Hz, 2H), 7.13e7.15 (m, 3H), 7.06 (d, J ¼ 8.5 Hz, 1H), 4.26 (t,
J ¼ 7.0 Hz, 3H), 1.94e2.00 (m, 4H), 1.88e92 (m, 4H), 1.76e1.86 (m,
2H), 1.30e1.33 (m, 2H), 0.87 (t, J ¼ 7.5 Hz, 3H), 0.38 (t, J ¼ 7.0 Hz,
12H); 13C NMR (DMSO-d6, 125.77 MHz) d 166.0, 162.8, 152.6, 152.2,
150.7, 149.1, 147.3, 147.2, 146.8, 146.5, 141.8, 141.3, 140.9, 140.7, 136.1,
133.8, 133.5, 129.5, 128.3, 127.0, 126.5, 125.2, 124.7, 123.0, 122.7,
122.4, 120.8, 120.3, 119.2, 118.3, 117.5, 117.1, 116.1, 107.0, 105.8, 103.9,
55.6, 41.8, 31.9, 30.5, 19.7, 13.5, 8.4; HRMS calcd for C62H55N3O2S2Na
[M þ Na]þ m/z 960.3628, found 960.3618.
2.3. Computational methods
DFT calculations were performed using Gaussian 09 program
package. The ground-state geometry of the dyes were optimized
without any symmetry constraints employing a Becke's [27] hybrid
correlation functional B3LYP [28] with 6e31 g (d,p) basis set for all
atoms. Vibrational analysis of the optimized structures was used to
confirm the structure. The vertical excitation energies and oscillator
strengths for the lowest 10 singletesinglet transitions for the
optimized geometry in the ground state were computed by TD-DFT
calculations using the same basis set with two different hybrid
functionals B3LYP [28] and MPW1K [29]. MPW1K functional was
found to yield good estimate for the vertical excitation energies of
the dyes.
2.4. DSSC fabrication and characterization
The photoanodes were prepared by coating transparent and
scattering layers of TiO2 with different sizes by doctor blade
method on a pretreated fluorine-doped SnO2 conducting glass
(FTO, 7 U sq.1, transmittance ~80%, NSG America, Inc., New Jersey,
USA). The transparent layer contained 20 nm sized TiO2 and
measured ~12 mm thickness while the ~4 mm thick scattering layer
was made from 300 nm sized TiO2. The dyes were adsorbed by
immersing the TiO2 film in a 3  104 M dye solution for 24 h, at
room temperature. A solvent mixture containing acetonitrile, tert-
butyl alcohol and dimethyl sulfoxide (volume ratio of 3.5:3.5:3)
was used to prepare the dye bath. The absorption spectrum of the
dye coated TiO2 was measured by using a JASCO UVevisible spec-
trophotometer (V-570) equipped with an integrating sphere. The
TiO2/dye electrode was placed on a platinum-sputtered ITO coated
glass (7 U sq.1, Ritek Corporation, Hsinchu, Taiwan). Then the two
electrodes were sandwiched with a 25 mm-thick Surlyn® (SX1170-
25, Solaronix S.A., Aubonne, Switzerland) at the edges. A mixture of
1-propyl-2,3-dimethylimidazolium iodide (1.2 M), iodine
(0.035 M), tert-butylpyridine (0.5 M) and guanidine thiocyanate
(0.1 M) dissolved in acetonitrile/3-methoxypropionitrile mixture
(8:2) served as electrolyte. It was injected into the gap between the
electrodes and sealed to obtain the working DSSC.
The active area of the DSSC was restricted to 0.16 cm2 by using a
mask. A class-A solar simulator (XES-301S, AM 1.5 G, San-Ei Electric
Co., Ltd.) was used to illuminate the device. A standard silicon cell
(PECSI01, Peccell Technologies, Inc.) was used to calibrate the incident
light intensity and maintained at 100 mW cm2. Current-voltage
characteristics of the DSSC were recorded with a potentiostat/
158 K.R. Justin Thomas et al. / Dyes and Pigments 123 (2015) 154e165

galvanostat (PGSTAT 30, Autolab, Eco-Chemie, the Netherlands).

Electrochemical impedance spectral (EIS) analysis of the DSSCs was
performed by using a potentiostat/galvanostat equipped with an FRA2
module. The applied bias voltage was set at the open-circuit voltage of
the DSSC. IPCE spectrum was obtained at short-circuit condition using
a monochromated (Oriel Instrument, model 74100) light. The IPCE (l)
is defined by IPCE (l) ¼ 1240 (JSC/l4), where l is the wavelength, JSC is
short-circuit photocurrent density (mA cm2) recorded with a
potentiostat/galvanostat, and 4 is the incident radiative flux (W m2)
measured with an optical detector (Oriel Instrument, model 71580)
and a power meter (Oriel Instrument, model 70310).

3. Results and discussion

3.1. Synthesis and characterization

The structures of the new dyes containing carbazole linker and

fluoreneamine-based donor are displayed in Fig. 1 and the syn-
thetic pathway used to obtain them illustrated in Scheme 1. In the Fig. 2. Absorption spectra of the dyes recorded in dichloromethane.

first, the secondary amines (2a and 2b) were synthesized by

following Buchwald-Hartwig CeN coupling [30] protocol from a
suitable bromofluorene and primary amine in moderate yields.
Then the secondary amines (2a and 2b) were treated with a slight
excess of 2,7-dibromo-9-butyl-9H-carbazole [24] (1) using palla-
dium catalyzed CeN coupling conditions to obtain the precursor
compounds 3a and 3b in good yields. The aldehydes 4 and 5 were
prepared by Stille coupling reaction [31] of 3 with tin reagents of
the suitably protected thienyl aldehydes and followed by acidic
hydrolysis. The aldehydes 4 and 5 were finally converted to the
corresponding cyanoacrylic acid derivatives 6 and 7 by Knoevena-
gel condensation [32] with cyanoacetic acid. The dyes are brown to
black in color and soluble in common organic solvents such as
cyclohexane (CH), toluene (Tol), dichloromethane (DCM), tetrahy-
drofuran (THF), N,N-dimethylformamide (DMF) and acetonitrile
(ACN). All the compounds were thoroughly characterized by IR,
NMR (1H and 13C) and mass spectral methods. The proposed
structures of the dyes are consistent with their spectral data.
3.2. Photophysical properties
The absorption spectra of the dyes (6 and 7), recorded in DCM,
are displayed in Fig. 2 and the relevant photophysical data compiled
in Table 1. For comparison the absorption spectra of the bromo- and
aldehyde-precursors were also reported.
All dyes exhibited three major distinguishable absorption peaks
at ~260, ~360 and ~480 nm, respectively. The highest energy peak at
~265 nm is attributed to the p-p* transition localized on the dia-
rylamine and carbazole units [23,33]. The middle wavelength range
absorption occurring at 310e410 nm is probably originating from
the p-p* transition of the conjugation pathway in the dyes [9b,22].
Interestingly, this absorption inherited large molar extinction co-
efficients on incorporation of fluorene in the donor segment and
displayed a slight red-shift on introduction of additional thiophene
in the conjugation pathway. The longer wavelength absorption is
assigned to the charge transfer transition from the triarylamine
donor to the cyanoacrylic acid acceptor. The introduction of fluorene
(compare C1 with 6a and 6b and C2 with 7a and 7b) increased the
donor strength which led to strong donor-acceptor interaction
and led to red-shift in the absorption. The dyes (6b and 7b) con-
taining difluorenylamine donor showed the most red shifted
absorption in the series highlighting the benefit of fluorene-based
donors. In brief, the absorption spectral parameters of the dyes
are reflective of the donor strength of the diarylamine segment,
diphenylamine < fluorenylphenylamine < difluorenylamine.

Scheme 1. Synthetic pathway used to obtain the new dyes.

 K.R. Justin Thomas et al. / Dyes and Pigments 123 (2015) 154e165 159

Table 1
Optical and electrochemical properties of the dyes and related compounds recorded in dichloromethane.

Compd. labs, nm (εmax  103 M1 cm1) lem, nm Eoxa, V (DEP, mV) HOMOb, eV LUMOc, eV E0-0d, eV Eoxe, V E*oxf, V DGinjg, V
(vs NHE) (vs NHE)

3a 342 (26.3), 273 (29.1) 412 0.32 (83), 0.82 5.12 1.93 3.19 1.09 2.10 1.60
3b 370 (38.4), 275 (32.3) 423 0.26 (75), 0.80 5.06 1.97 3.09 1.03 2.06 1.56
4a 422 (31.2), 333 (31.0), 274 (32.9), 575 0.31 (69), 0.80 5.11 2.57 2.54 1.08 1.46 0.96
253 (31.9)
4b 432 (26.3), 368 (30.5), 276 (30.7), 579 0.25 (60), 0.80 5.05 2.57 2.48 1.02 1.46 0.96
255 (31.0)
5a 431 (30.4), 350 (27.0), 271 (28.3) 496 0.29 (63), 0.72 5.09 2.44 2.65 1.06 1.59 1.09
5b 439 (26.7), 372 (33.8), 272 (26.9) 515 0.23 (64), 0.80 5.03 2.45 2.58 1.00 1.58 1.08
6a 483 (25.1), 363 (27.9), 268(33.7) 575 0.31 (57), 0.78 5.11 2.78 2.30 1.08 1.22 0.72
7a 490 (32.6), 383 (29.3), 352 (27.8), 581 0.28 (54), 0.70 5.08 2.81 2.27 1.05 1.22 0.72
263 (38.7)
6b 497 (29.2), 374 (53.5), 266 (43.3) 577 0.26 (61), 0.77 5.06 2.75 2.31 1.03 1.28 0.78
7b 497 (31.9), 378 (47.5), 262 (43.0) 578 0.22 (57), 0.69 5.02 2.74 2.28 0.99 1.29 0.79
a
Oxidation potentials are reported with reference to the ferrocene internal standard.
b
Deduced from the oxidation potential using the formula HOMO ¼ 4.8 þ Eox.
c
Deduced using the formula LUMO ¼ HOMO - E0-0.
d
Calculated from intersection of absorption and emission spectra.
e
Calculated by addition of solvent correction (0.77 V for DCM) to EOX.
f
Calculated from Eox* ¼ EoxeE0-0.
g
DGinj ¼ ECB - Eox*.

Consequently, the overall trend observed for absorption maximum
of dyes is: C1 (472 nm) < 6a (483 nm) < C2 (489 nm) < 7a
(490 nm) < 6b (497 nm) < 7b (498 nm). The bithiophene containing
dyes (7a and 7b) exhibited red-shifted broad absorption with high
molar extinction coefficients when compared to their thiophene
analogs (6a and 6b), respectively. This suggests that the electron
richness of the conjugation pathway also affects the absorption
parameters of the organic dyes in addition to the strength of the
donor alterend by the fluorene incorporation. This establishes the
benefit of 2,7-carbazole linkage in mediating donor-acceptor
interaction due to its electron richness and effective electronic
coupling. Also, the new dyes showed promising absorption
parameters when compared to the structurally similar dyes
(Fig. 3) containing fluorene at the periphery of the donor (C1FL and
C2FL) [33].
It is interesting to compare the absorption properties of the dyes
with the structurally similar dyes (Fig. 3) containing difluorenyl-
amine donor and different linkers such as phenyl (JK-1 and JK-2)
[9b], benzo[b]furan (JKBF1 and JKBF2) [34], indeno[1,2-b]thio-
phene (JK-225) [35], indeno[1,2-b]thieno[2,3-d]thiophene (JK-276)
[36] and fluorene (JA1 and JA2) [7f]. The preset dyes (7a and 7b)
exhibit absorption maxima at wavelength longer than the dyes
containing phenyl, benzo[b]furan, indeno[1,2-b]thiophene, indeno
[1,2-b]thieno[2,3-d]thiophene linkers. But, the peak positions are
slightly blue-shifted than those of the dyes containing fluorene in
the conjugation pathway [22]. These observations suggest that the
auxiliary effect of fluorene segment is less significant than the
tremendous impact of fluoreneamine donor. All dyes exhibited
higher molar extinction coefficients (25,100 M1 cm1 to
32,600 M1 cm1) than the promising ruthenium-based organo-
metallic dyes N3 and N719 [37].
The charge transfer nature of the longer wavelength absorption
in the dyes is revealed by the following observations: (i) Addition of
trifluoroacetic acid (TFA) or triethylamine (TEA) to the dichloro-
methane solutions of the dyes produced a bathochromic shift or
hypsochromic shift as illustrated in Fig. 4a for the dye 6b. This

Fig. 3. Structures of the dyes containing various arylamine donor units.

160 K.R. Justin Thomas et al. / Dyes and Pigments 123 (2015) 154e165

Fig. 5. Absorption spectra of the dyes anchored on TiO2 films.

Absorption spectra of the dyes anchored on TiO2 are displayed in

Fig. 5. The absorption spectra of the thiophene-linked dyes (6a and
6b) are blue-shifted when compared to their absorption recorded
in solution. However, the bithiophene-linked dyes (7a and 7b)
showed considerable broadening and red-shift when compared to
their solution spectra. This probably suggests that the dyes 6a and
6b are not aggregating at the surface of TiO2 and the blue-shift may
be due to the deprotonation of carboxylic acid on interaction of the
dye with TiO2 [40,42]. On the contrary, the red-shift realized for the
dyes 7a and 7b indicate a considerable J-aggregate formation [43].
It is speculated that the elongation of the conjugation by the
bithiophene segment provides sufficient planar environment for
intermolecular stacking interactions.

Fig. 4. Absorption spectra of the dye 6b recorded in (a) dichloromethane and after
3.3. Electrochemical properties
addition of TEA/TFA and (b) different solvents.

The redox propensity of the dyes was estimated by electro-

bathochromic/hypsochromic shift is attributed to the modulation chemical measurements in dichloromethane. Cyclic voltammograms
of the acceptor strength due to the protonation/deprotonation of
carboxylic acid unit [38]. (ii) All dyes exhibited a negative sol-
vatochromism as shown in Fig. 4b for a representative dye. This
clearly indicates that the dyes are effectively solvated by the polar
solvents in the ground state suggesting a polarized structure
resulting from the charge transfer from the amine donor to the
cyanoacrylic acid acceptor. Effective solvation of the dyes with polar
solvents increases the energy gap and results blue shift in the ab-
sorption [39]. More prominent blue-shift observed in DMF is
probably caused by the deprotonation of carboxylic acid unit in the
dyes [40]. Similarly, an unusual blue shift in THF is ascribed to the
hydrogen bonding interaction between the dye and solvent which
weakens the acceptor ability of the cyanoacrylic acid unit [40]. In
contrast, a significant red-shift observed in chloro-solvents such as
dichloromethane and chloroform arises due to the rapid relaxation
of polarizable electrons in the excited state [41]. (iii) Finally, all
dyes possessed comparatively red-shifted longest wavelength
absorption when compared to the corresponding bromo- and
aldehyde derivatives. Since Br, CHO and cyanoacrylic acid units
are not expected to affect the conjugation length significantly,
the observed huge shifts in the absorption maximum are
believed to be arising from the difference in the acceptor strength
(Br < CHO < cyanoacrylic acid). Fig. 6. Cyclic voltammograms of the dyes recorded in dichloromethane.
 K.R. Justin Thomas et al. / Dyes and Pigments 123 (2015) 154e165 161

(6b and 7b) possessed more negative excited state oxidation po-
tentials and less positive ground state oxidation potentials. Thus,
the difluorenylamine donor containing dyes 6b and 7b are pre-
dicted to exhibit facile regeneration by the redox electrolyte and
high electron injection efficiency in the series. In corroboration
with this ascertain, the calculated DGinj of the dyes assume the
order: C2 (0.67 V) < C1 (0.68 V) < 6a ¼ 7a (0.72 V) < 6b
(0.78 V) < 7b (0.79 V).

3.4. Theoretical calculations

Fig. 7. Energy level diagram depicting correlation between the redox potentials of the
materials used in DSSC.
of the dyes are displayed in Fig. 6 and the pertinent data listed in
Table 1.
All dyes showed one quasi-reversible oxidation process corre-
sponding to the removal of electron from the amine donor and an
irreversible oxidation wave originating from the conjugation
pathway. The first oxidation potential of the dyes decreased on
introduction of fluorene in the donor segment for the similar
conjugation pathway (6a > 6b or 7a > 7b). For the same donor, the
oxidation potential decreased on elongation of the conjugation
with thiophene introduction (7 < 6). This suggests that incorpo-
ration of fluorene and thiophene increases the electron richness of
the molecules which results in facile oxidation. Dyes 6b and 7b
exhibited low oxidation potentials than the closely related dyes
C1FL and C2FL which featured peripheral fluorene chromophore
on the diphenylamine donor [33a].
In order to ascertain the electron injection and dye regenera-
tion feasibility, the ground and excited state oxidation potentials
relative to normal hydrogen electrode (NHE) was calculated from
the experimental redox potentials of the dyes. The comparison of
the redox potentials of the dyes and electrolyte and conduction
band of TiO2 is shown in Fig. 7. In general, the ground state
oxidation potentials for these dyes are in the range of
1.03 Ve1.15 V vs NHE, which are more positive than the redox
potential of Ie/Ie3 redox couple, thus favor efficient regeneration of
the dyes from the oxidized form by the electrolyte [4a]. Similarly,
the excited-state oxidation potentials (1.22 V to 1.29 V) of the
sensitizers are more negative than the conduction band of the
TiO2 which is thermodynamically favorable for electron injection
from the excited state of the dye into the conduction band of the
TiO2 [44]. Fluorene units has been found to affect the ground and
excited state oxidation potentials of the dyes significantly [33a].
Introduction of fluorene in the donor negatively shifts the oxida-
tion potentials. So the dyes containing difluorenylamine donor
To gain further insights into the electronic structure of the
compounds density functional theory (DFT) calculations were
performed on the dyes. The geometry of the compounds in the
ground state in gas phase was optimized by DFT using 6-31 þ G (d,
p) basis set and B3LYP [28], hybrid correlation functional. The
vertical energies were computed using the time dependent density
functional theory in the same level for ground state optimized
structures with MPW1K [29] functional. The computed vertical
excitation energies and their molecular orbital contributions are
listed in Table 2. The frontier molecular orbitals (HOMO and LUMO)
of the dyes are displayed in Fig. 8.
The HOMO of the dyes is mainly located on the triarylamine
segment comprising carbazole and the LUMO of the dyes distrib-
uted on cyanoacrylic acid and spread up to oligothiophene moiety.
The longer wavelength absorption corresponds to the electronic
excitation from HOMO to LUMO. From these results, it is clear that
the longer wavelength absorption is charge transfer in nature and it
would lead to charge migration from the triarylamine donor to the
cyanoacrylic acid acceptor on photoexcitation. Such a photon
induced charge transfer is desirous to inject an electron from the
photo-excited dye into the conduction band of TiO2. Overlap of
HOMO and LUMO is minimal in the bithiophene-based dyes (7a
and 7b). This indicates that more effective charge separation is
possible in bithiophene dyes. The HOMO-1 is contributed signifi-
cantly by the carbazole linker in the thiophene linked dyes (6a and
6b), while it is spread into the bithiophene unit in dyes 7a and 7b.
On this basis it can be proposed that the second oxidation of the
dyes predominantly occur due to the removal of electron from the
conjugation pathway. The second prominent absorption in the dyes
is contributed by the electronic excitation from HOMO-1 to LUMO.
So it can be safely assumed that the absorption due to the charge
transfer and p-p* transitions can lead to electron injection from the
dye into the conduction band of TiO2 [33b]. The absorption peak
positions estimated from MPW1K [29] calculations closely
resemble the experimental values. The calculated trend observed
for dyes is 7a < 6a and 7b < 6b for thiophene and bithiophene
containing dyes respectively and this matches with the experi-
mental data.

Table 2
Computed vertical transition energies and their oscillator strengths, assignments, dipole moments and band gaps for the dyes at the MPW1K/6-31G(d,p) in THF.

Dye l, nm f Assignments mg, D HOMO, eV LUMO, eV Eg, eV

6a 440.7 1.24 HOMO / LUMO (81%), HOMO-2 / LUMO (13%) 11.82 5.79 2.15 3.64
349.2 0.41 HOMO-2 / LUMO (69%), HOMO / LUMO (14%),
HOMO-3 / LUMO (12%)
6b 448.0 1.14 HOMO / LUMO (82%), HOMO-2 / LUMO (11%) 11.10 5.70 2.15 3.54
361.1 0.24 HOMO-1 / LUMO (82%)
7a 462.1 1.64 HOMO / LUMO (63%), HOMO-1 / LUMO (30%) 7.86 5.74 2.29 3.45
386.0 0.27 HOMO-1 / LUMO (57%), HOMO / LUMO (33%)
7b 464.8 1.54 HOMO / LUMO (64%), HOMO-1 / LUMO (29%) 7.65 5.66 2.29 3.37
394.1 0.40 HOMO-1 / LUMO (58%), HOMO / LUMO (32%)
162 K.R. Justin Thomas et al. / Dyes and Pigments 123 (2015) 154e165

Fig. 8. Energies and the electronic distribution of the frontier molecular orbitals of the dyes (6 and 7) computed in THF using TDDFT/MPW1K/6-31G (d, p).

3.5. DSSC characteristics 6a < 7a < 7b < 6b. This indicates a relatively slower recombination
for the difluorenylamine-based dyes 6b and 7b.
The photovoltaic performances of the dyes (6 and 7) were tested The Nyquist plots constructed for the devices under illumina-
by using them as sensitizers in Grӓtzel photo electrochemical cells tion conditions (Fig. 11a) are used to ascertain the differences in
[44a]. For comparison, dyes C1 and C2 were also examined under the photocurrent generation. The middle frequency semicircle
the same conditions. The IeV curves and IPCE spectra of DSSC
fabricated using these dyes are displayed in Fig. 9. All the dyes,
except 6a, showed promising light-to-current conversion over 70%
in the region 350e550 nm. The dye 7a exhibited superior IPCE in
the series which is consistent with the absorption spectra of the dye
anchored on TiO2 as well as solution. Thus, it has achieved highest
JSC ¼ 16.20 mA cm2 which led to high power conversion efficiency
(PCE) of 6.10% Table 3. But, the dye 6b exhibited highest PCE of
6.44% owing to its relatively high VOC (666 mV) even though the JSC
(15.60 mA cm2) is slightly lower than that observed for 7a. The
inferior performance of 6a might be due to its low molar extinction
coefficient for the CT transition and lowest recombination resis-
tance [7b,7f,45].
Light harvesting efficiency affects the JSC and followed by the
efficiency of the device. The JSC follows an order,
6a < 7b < 6b < 7a. The trend is consistent with the IPCE spectra of
the devices and the larger photocurrent for the dye 7a and 6b is
due to the high response in the IPCE spectrum. For the fluo-
renylphenylamine donor containing dyes (6a and 7a) bithiophene
conjugation (7a) benefits light harvesting and leads to better JSC.
But, the reverse phenomenon is observed for the difluorenylamine
donor (6b and 7b). On comparing the thiophene conjugated de-
rivatives (6a and 6b) high JSC observed for 6b is reflective of its
light-harvesting properties (Fig. 2). Here, the introduction of
additional fluorene on the donor segment probably increases the
donor strength and consequently the donor-acceptor interactions.
However, in the case of bithiophene derivatives (7a and 7b) better
JSC is observed for 7a. Since, bithiophene is sufficiently electron-
rich, additional fluorene does not affect the light-harvesting
properties significantly (Fig. 2). Interestingly, 7a showed better
dye-loading when compared to 7b. Unsymmetrical dyes are re-
ported to yield very compact arrangement in the TiO2 surface and
thus increase the dye-loading [7f]. The higher JSC observed for 7a
may be due to the availability of more molecules for light ab-
sorption at the TiO2 surface. Also, there is a difference in the
charge transfer resistance also (see below).
The open circuit voltage for the devices follows an order:
6a < 7a < 7b < 6b. High VOC observed for the difluorenylamine donor
containing compound is understandable on considering the bulki-
ness which probably prevents the electrolyte approaching the TiO2
layer [9b]. This is further evidenced from the Nyquist plots con-
structed for the DSSCs under dark conditions (Fig. 10). The radius of
the intermediate frequency larger semicircle corresponding to the Fig. 9. (a) IeV characteristics and (b) IPCE spectra of the devices fabricated using the
recombination of electrons with the electrolyte assumes the order: dyes.
 K.R. Justin Thomas et al. / Dyes and Pigments 123 (2015) 154e165 163

Table 3
Performance parameters of the DSSCs fabricated using the dyes.

Dye h (%) VOC, mV JSC, mA cm2 ff Rct2, ohm fmax, Hz te (ms) Rrec, ohm Dye loading, mmol cm3

6a 2.98 562 8.25 0.64 29.29 137.72 1.16 14.71 56.7

6b 6.44 666 15.60 0.62 14.76 18.92 8.41 50.00 52.5
7a 6.10 616 16.20 0.61 13.33 41.88 3.80 22.35 48.9
7b 4.77 630 12.50 0.61 20.00 62.37 2.55 26.47 41.8
N719 9.12 744 17.80 0.69 12.13 12.74 12.50 84.71 e

represents the charge transport resistance (Rct2) across the TiO2/ incorporation. In addition, the bulkiness of the difluorenylamine
dye/electrolyte interface and it follows the order: segment has been found to retard the close approach of electrolyte
7a < 6b < 7b < 6a. This suggests a favorable charge transport for 7a at the TiO2 surface which suppressed the detrimental electron
and high hindrance for 6a. This trend is grossly consistent with the recombination process. Among the series, a dye possessing
JSC order: 6a < 7b < 6b < 7a. Despite high Rct2, high JSC observed for difluorenylamine donor and carbazolylthiophene conjugation
6b over 7a is probably due to the high electron recombination rate pathway (6b) exhibited impressive PCE (6.44%) which is better than
of 7a which probably depletes the harvested electron density in the the reported diphenylamine-based dye [23]. In this study, we have
conduction band of TiO2 [7f]. shown that further improvement in the light-harvesting ability of a
Bode-phase plots of the dyes are displayed in Fig. 11b. The promising dye can be achieved by slight structural variation in the
electron life time (te) is extracted from the angular frequency (umin) donor segment.
of the mid frequency peak in the Bode phase plot using te ¼ 1/umin
[46]. The te assumed an order 6b > 7a > 7b > 6a. The significantly
increased lifetime of an electron for the dye 6b is caused by the
suppression of the recombination of electrons due to the hydro-
phobic repulsion exerted by the difluorenylamine segment [47].
Thus, the less hindrance for the charge transfer and more retar-
dation for electron recombination for 6b are responsible for its high
PCE (6.44%).

4. Conclusions

We have successfully synthesized and characterized a new set of

organic dyes containing 2,7-carbazole linker, fluorenylamine donor
and cyanoacrylic acid acceptor. The incorporation of fluorene in the
donor segment plays a profound effect on the optical and electro-
chemical properties of the dyes which manifested in the fine-
tuning of the frontier molecular orbitals desirous to enhance the
electron injection and dye regeneration. The new dyes exhibited
red-shifted absorption when compared to the diphenylamine-
based dyes containing 2,7-carbazole linker [23]. Also, the removal
of electron from the dye is enhanced due to the fluorene

Fig. 11. Nyquist (a) and (b) Bode-phase plots for the DSSCs measured under
Fig. 10. Nyquist plots observed for the DSSCs measured under dark. illumination.
164 K.R. Justin Thomas et al. / Dyes and Pigments 123 (2015) 154e165
Acknowledgment
KRJT is thankful to DST, New Delhi for generous financial
assistance (Ref. No. DST/TSG/PT/2013/09). AV acknowledges a
research fellowship from UGC, New Delhi. We are also thankful to
DST for the purchase of ESI mass spectrometer by a generous FIST
grant to the Chemistry Department, IIT Roorkee.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.dyepig.2015.07.034.
References
[1] (a) Zhu X-H, Peng J, Cao Y, Roncali J. Solution-processable single-material
molecular emitters for organic light-emitting devices. Chem Soc Rev
2011;40:3509e24.
(b) Moonsin P, Prachumrak N, Namuangruk S, Jungsuttiwong S, Keawin T,
Sudyoadsuk T, et al. Bifunctional oligofluorene-cored carbazole dendrimers as
solution-processed blue emitters and hole transporters for electroluminescent
devices. J Mater Chem C 2014;2:5540e52.
(c) Leijtens T, Ding I-K, Giovenzana T, Bloking JT, McGehee MD, Sellinger A.
Hole transport materials with low glass transition temperatures and high
solubility for application in solid-state dye-sensitized solar cells. ACS Nano
2012;6:1455e62.
[2] (a) Mishra A, Ba€uerle P. Small molecule organic semiconductors on the move:
promises for future solar energy technology. Angew Chem Int Ed 2012;51:
2020e67.
(b) Takacs CJ, Sun Y, Welch GC, Perez LA, Liu X, Wen W, et al. Self-assembly,
and dipole-dipole interactions of isomorphic narrow-band-gap molecules.
J Am Chem Soc 2012;134:16597e606.
[3] (a) Qin P, Kast H, Nazeeruddin MK, Zakeeruddin SM, Mishra A, Ba €uerle P, et al.
Low band gap S,N-heteroacene-based oligothiophenes as hole-transporting
and light absorbing materials for efficient perovskite-based solar cells. En-
ergy Environ Sci 2014;7:2981e5.
(b) Jeon NJ, Lee HG, Kim YC, Seo J, Noh JH, Lee J, et al. o-Methoxy substituents
in Spiro-OMeTAD for efficient inorganic-organic hybrid perovskite solar cells.
J Am Chem Soc 2014;136:7837e40.
(c) Sung SD, Kang MS, Choi IT, Kim HM, Kim H, Hong M, et al. 14.8% Perovskite
solar cells employing carbazole derivatives as hole transporting materials.
Chem Commun 2014;50:14161e3.
(d) Choi H, Park S, Paek S, Ekanayake P, Nazeeruddin MK, Ko J. Efficient star-
shaped hole transporting materials with diphenylethenyl side arms for an
efficient perovskite solar cell. J Mater Chem A 2014;2:19136e40.
[4] (a) Hagfeldt A, Boschloo G, Sun L, Kloo L, Pettersson H. Dye-sensitized solar
cells. Chem Rev 2010;110:6595e663.
(b) Liang M, Chen J. Arylamine organic dyes for dye-sensitized solar cells.
Chem Soc Rev 2013;42:3453e88.
(c) Ooyama Y, Harima Y. Photophysical and electrochemical properties, and
molecular structures of organic dyes for dyesensitized solar cells. Chem-
PhysChem 2012;13:4032e80.
(d) Mishra A, Fischer MKR, B€ auerle P. Metal-free organic dyes for dye-
sensitized solar cells: from structure: property relationships to design rules.
Angew Chem Int Ed 2009;48:2474e99.
(e) Haid S, Marszalek M, Mishra A, Wielopolski M, Joe €l T, Moser J-E, et al.
Significant improvement of dye-sensitized solar cell performance by small
structural modification in p-conjugated donor-acceptor dyes. Adv Funct
Mater 2012;22:1291e302.
[5] (a) Murphy AR, Fre chet JMJ. Organic semiconducting oligomers for use in thin
film transistors. Chem Rev 2007;107:1066e96.
(b) Zaumseil J, Sirringhaus H. Electron and ambipolar transport in organic
field-effect transistors. Chem Rev 2007;107:1296e323.
[6] (a) Sumalekshmy S, Fahrni CJ. Metal-ion-responsive fluorescent probes for
two-photon excitation microscopy. Chem Mater 2011;23:483e500.
(b) He GS, Tan L-S, Zheng Q, Prasad PN. Multiphoton absorbing materials:
molecular designs, characterizations, and applications. Chem Rev 2008;108:
1245e330.
[7] (a) Ooyama Y, Yamada T, Fujita T, Harima Y, Ohshita J. Development of D-p-
Cat fluorescent dyes with a catechol group for dye-sensitized solar cells based
on dye-to-TiO2 charge transfer. J Mater Chem A 2014;2:8500e11.
(b) Yang C-J, Chang YJ, Watanabe M, Hon Y-S, Chow TJ. Phenothiazine de-
rivatives as organic sensitizers for highly efficient dye-sensitized solar cells.
J Mater Chem 2012;22:4040e9.
(c) Tang J, Hua J, Wu W, Li J, Jin Z, Long Y, et al. New starburst sensitizer with
carbazole antennas for efficient and stable dye-sensitized solar cells. Energy
Environ Sci 2010;3:1736e45.
(d) Thomas KRJ, Kapoor N, Lee C-P, Ho K-C. Organic dyes containing
pyrenylamine-based cascade donor systems with different aromatic p linkers
for dye-sensitized solar cells: optical, electrochemical, and device
characteristics. Chem Asian J 2012;7:738e50.
(e) Hung W-I, Liao Y-Y, Hsu C-Y, Chou H-H, Lee T-H, Kao W-S, et al. High-
performance dye-sensitized solar cells based on phenothiazine dyes con-
taining double anchors and thiophene spacers. Chem Asian J 2014;9:357e66.
(f) Baheti A, Thomas KRJ, Lee C-P, Li C-T, Ho K-C. Organic dyes containing-
fluoren-9-ylidene chromophores for efficient dye-sensitized solar cells.
J Mater Chem A 2014;2:5766e79.
(g) Lu X, Feng Q, Lan T, Zhou G, Wang Z-S. Molecular engineering of
quinoxaline-based organic sensitizers for highly efficient and stable dye-
sensitized solar cells. Chem Mater 2012;24:3179e87.
[8] (a) Chu H-C, Sahu D, Hsu Y-C, Padhy H, Patra D, Lin J-T, et al. Structural
planarity and conjugation effects of novel symmetrical acceptor-donor-
acceptor organic sensitizers on dye-sensitized solar cells. Dyes Pigm
2012;93:1488e97.
(b) Zhang H, Fan J, Iqbal Z, Kuang D-B, Wang L, Meier H, et al. Novel dithieno
[3,2-b:20 ,30 -d]pyrrole-based organic dyes with high molar extinction coeffi-
cient for dye-sensitized solar cells. Org Electron 2013;14:2071e81.
(c) Lin RY-Y, Wu F-L, Chang C-H, Chou H-H, Chuang T-M, Chu T-C, et al. Y-
shaped metal-free D-p-(A)2 sensitizers for highperformance dye-sensitized
solar cells. J Mater Chem A 2014;2:3092e101.
(d) Li Q, Shi J, Li H, Li S, Zhong C, Guo F, et al. Novel pyrrole-based dyes for dye-
sensitized solar cells: from rod-shape to ‘‘H’’ type. J Mater Chem 2012;22:
6689e96.
(e) Seo KD, You BS, Choi IT, Ju MJ, You M, Kang HS, et al. Dye-sensitized solar
cells based on organic dual-channel anchorable dyes with well-defined core
bridge structures. ChemSusChem 2013;6:2069e73.
[9] (a) Thomas KRJ, Lin JT, Hsu Y-C, Ho K-C. Fluorene based organic dye for dye
sensitized solar cells: structure-property relationships. Chem Commun 2005:
4098e100.
(b) Kim S, Lee JW, Kang SO, Ko J, Yum J-H, Fantacci S, et al. Molecular engi-
neering of organic sensitizers for solar cell applications. J Am Chem Soc
2006;128:16701e7.
(c) Nguyen WH, Bailie CD, Burschka J, Moehl T, Gra €tzel M, McGehee MD, et al.
Molecular engineering of organic dyes for improved recombination lifetime in
solid-state dye-sensitized solar cells. Chem Mater 2013;25:1519e25.
[10] (a) Hua Y, Chang S, Huang D, Zhou X, Zhu X, Zhao J, et al. Significant
improvement of dye-sensitized solar cell performance using simple
phenothiazine-based dyes. Chem Mater 2013;25:2146e53.
(b) Bodedla GB, Thomas KRJ, Li C-T, Ho K-C. Functional tuning of
phenothiazine-based dyes by a benzimidazole auxiliary chromophore: an
account of optical and photovoltaic studies. RSC Adv 2014;4:53588e601.
[11] (a) Tian H, Bora I, Jiang X, Gabrielsson E, Karlsson KM, Hagfeldt A, et al.
Modifying organic phenoxazine dyes for efficient dye-sensitized solar cells.
J Mater Chem 2011;21:12462e72.
(b) Tan H, Pan C, Wang G, Wu Y, Zhang Y, Zou Y, et al. Phenoxazine-based
organic dyes with different chromophores for dye-sensitized solar cells. Org
Electron 2013;14:2795e801.
[12] (a) Ito S, Miura H, Uchida S, Takata M, Sumioka K, Liska P, et al. High-con-
version-efficiency organic dye-sensitized solar cells with a novel indoline dye.
Chem Commun 2008:5194e6.
(b) Horiuchi T, Miura H, Sumioka K, Uchida S. High efficiency of dye-sensitized
solar cells based on metal-free indoline dyes. J Am Chem Soc 2004;126:
12218e9.
(c) Wu Y, Marszalek M, Zakeeruddin SM, Zhang Q, Tian H, Gr€ atzel M, et al.
High-conversion-efficiency organic dye-sensitized solar cells: molecular en-
gineering on D-A-p-A featured organic indoline dyes. Energy Environ Sci
2012;5:8261e72.
[13] (a) Hara K, Wang ZS, Sato T, Furube A, Katoh R, Sugihara H, et al. Oligothio-
phene-containing coumarin dyes for efficient dye-sensitized solar cells. J Phys
Chem B 2005;109:15476e82.
(b) Alibabaei L, Kim J-H, Wang M, Pootrakulchote N, Teuscher J, Censo DD,
et al. Molecular design of metal-free D-p-A substituted sensitizers for dye-
sensitized solar cells. Energy Environ Sci 2010;3:1757e64.
[14] (a) Chen D-Y, Hsu Y-Y, Hsu H-C, Chen B-S, Lee Y-T, Fu H, et al. Organic dyes
with remarkably high absorptivity; all solid-state dye sensitized solar cell and
role of fluorine substitution. Chem Commun 2010;46:5256e8.
(b) Gao P, Kim YJ, Yum J-H, Holcombe TW, Nazeeruddin MK, Gra €tzel M. Facile
synthesis of a bulky BPTPA donor group suitable for cobalt electrolyte based
dye sensitized solar cells. J Mater Chem A 2013;1:5535e44.
[15] (a) Qin H, Wenger S, Xu M, Gao F, Jing X, Wang P, et al. An organic sensitizer
with a fused dithienothiophene unit for efficient and stable dye-sensitized
solar cells. J Am Chem Soc 2008;130:9202e3.
(b) Kwon T-H, Armel V, Nattestad A, MacFarlane DR, Bach U, Lind SJ, et al. An
organic sensitizer with a fused dithienothiophene unit for efficient and stable
dye-sensitized solar cells. J Org Chem 2011;76:4088e93.
[16] (a) Polander LE, Yella A, Teuscher J, Humphry-Baker R, Curchod BFE,
Astani NA, et al. Unravelling the potential for dithienopyrrole sensitizers in
dyesensitized solar cells. Chem Mater 2013;25:2642e8.
(b) Wang Z, Liang M, Hao Y, Zhang Y, Wang L, Sun Z, et al. Influence of the N-
heterocycle substituent of the dithieno[3,2-b:2ʹ,3ʹ-d]pyrrole (DTP) spacer as
well as sensitizer adsorption time on the photovoltaic properties of arylamine
organic dyes. J Mater Chem A 2013;1:11809e19.
(c) Wang Z, Liang M, Wang H, Wang P, Cheng F, Sun Z, et al. Joint electrical,
photophysical, and photovoltaic studies on truxene dye-sensitized solar cells:
Impact of arylamine electron donors. ChemSusChem 2014;7:795e803.
 K.R. Justin Thomas et al. / Dyes and Pigments 123 (2015) 154e165
(d) Zhang J, Yao Z, Cai Y, Yang L, Xu M, Li R, et al. Conjugated linker correlated
energetics and kinetics in dithienopyrrole dye-sensitized solar cells. Energy
Environ Sci 2013;6:1604e14.
[17] (a) Lu M, Liang M, Han H-Y, Sun Z, Xue S. Organic dyes incorporating bis-
hexapropyltruxeneamino moiety for efficient dye-sensitized solar cells.
J Phys Chem C 2011;115:274e81.
(b) Qian X, Zhu Y-Z, Song J, Gao X-P, Zheng J-Y. New donor-p-acceptor type
triazatruxene derivatives for highly efficient dye-sensitized solar cells. Org
Lett 2013;15:6034e7.
(c) Chai Q, Li W, Zhu S, Zhang Q, Zhu W. Influence of donor configurations on
photophysical, electrochemical, and photovoltaic performances in D-p-A
organic sensitizers. ACS Sustain Chem Eng 2014;2:239e47.
[18] Chang YJ, Chow TJ. Dye-sensitized solar cell utilizing organic dyads containing
triarylene conjugates. Tetrahedron 2009;65:4726e34.
[19] Wang M, Xu M, Shi D, Li R, Gao F, Zhang G, et al. High-performance liquid and
solid dye-sensitized solar cells based on a novel metal-free organic sensitizer.
Adv Mater 2008;20:4460e3.
[20] Kim C, Choi H, Kim S, Baik C, Song K, Kang M-S, et al. Molecular engineering of
organic sensitizers containing p-phenylene vinylene unit for dye-sensitized
solar cells. J Org Chem 2008;73:7072e9.
[21] (a) Kim J-J, Choi H, Lee J-W, Kang M-S, Song K, Kang SO, et al. A polymer gel
electrolyte to achieve ~ 6% power conversion efficiency with a novel organic
dye incorporating a low-band-gap chromophore. J Mater Chem 2008;18:
5223e9.
(b) Choi H, Kim J-J, Song K, Ko J, Nazeeruddin MK, Gr€ atzel M. Molecular en-
gineering of panchromatic unsymmetrical squaraines for dye-sensitized solar
cell applications. J Mater Chem 2010;20:3280e6.
[22] Baheti A, Gajjela SR, Balaya P, Thomas KRJ. Synthesis, optical, electrochemical
and photovoltaic properties of organic dyes containing trifluorenylamine
donors. Dyes Pigm 2015;113:78e86.
[23] Venkateswararao A, Thomas KRJ, Lee C-P, Ho K-C. Synthesis and character-
ization of organic dyes containing 2,7-disubstituted carbazole p-linker. Tet-
rahedron Lett 2013;54:3985e9.
[24] (a) Freeman AW, Urvoy M, Criswell ME. Triphenylphosphine-mediated
reductive cyclization of 2-nitrobiphenyls: a practical and convenient synthesis
of carbazoles. J Org Chem 2005;70:5014e9.
(b) Che Y, Gross DE, Huang H, Yang D, Yang X, Discekici E, et al. Diffusion-
controlled detection of trinitrotoluene: Interior nanoporous structure and low
highest occupied molecular orbital level of building blocks enhance selectivity
and sensitivity. J Am Chem Soc 2012;134:4978e82.
[25] Saroja G, Pingzhu Z, Ernsting NP, Liebscher J. Synthesis of alkylated amino-
fluorenes by palladium-catalyzed substitution at halofluorenes. J Org Chem
2004;69:987e90.
[26] Zhang H, Fan J, Dong H, Zhang S, Xu W, Wang J, et al. Fluorene-derived two-
photon fluorescent probes for specific and simultaneous bioimaging of
endoplasmic reticulum and lysosomes: group-effect and localization. J Mater
Chem B 2013;1:5450e5.
[27] (a) Becke AD. A new mixing of Hartree-Fock and local density-functional
theories. J Chem Phys 1993;98:1372e7.
(b) Lee C, Yang W, Parr RG. Development of the colle-salvetti correlation-
energy formula into a functional of the electron density. Phys Rev B 1988;37:
785e9.
[28] Parr RG, Yang W. Density-functional theory of the electronic structure of
molecules. Annu Rev Phys Chem 1995;46:701e28.
[29] Lynch BJ, Fast PL, Harris M, Truhlar DG. Adiabatic connection for kinetics.
J Phys Chem A 2000;104:4811e5.
[30] Hartwig JF. Transition metal catalyzed synthesis of arylamines and aryl ethers
from aryl halides and triflates: Scope and mechanism. Angew Chem Int Ed
1998;37:2047e67.
[31] Stille JK. The Palladium-catalyzed cross-coupling reactions of organotin re-
agents with organic electrophiles. Angew Chem Int Ed 1986;25:508e24.
[32] Knoevenagel E. Ueber eine darstellungsweise des benzylidenacetessigesters.
Chem Ber 1896;29:172e4.
[33] (a) Venkateswararao A, Thomas KRJ, Lee C-P, Ho K-C. Effect of auxiliary
chromophores on the optical, electrochemical, and photovoltaic properties of
carbazole-based dyes. Asian J Org Chem 2014;4:69e80.
(b) Venkateswararao A, Thomas KRJ, Li C-T, Ho K-C. Functional tuning of
View publication stats
165
organic dyes containing 2,7-carbazole and other electron-rich segments in the
conjugation pathway. RSC Adv 2015;5:17953e66.
[34] Jung I, Lee JK, Song KH, Song K, Kang SO, Ko J. Synthesis and photovoltaic
properties of efficient organic dyes containing the benzo[b]furan moiety for
solar cells. J Org Chem 2007;72:3652e8.
[35] Lim K, Kim C, Song J, Yu T, Lim W, Song K, et al. Enhancing the performance of
organic dye-sensitized solar cells via a slight structure modification. J Phys
Chem C 2011;115:22640e6.
[36] Choi H, Paek S, Lim K, Kim C, Kang M-S, Song K, et al. Molecular engineering of
organic sensitizers for highly efficient gel-state dye-sensitized solar cells.
J Mater Chem A 2013;1:8226e33.
[37] Nazeeruddin MK, Kay A, Rodicio I, Humphry-Baker R, Müller E, Liska P, et al.
Conversion of light to electricity by cis-X2bis(2,20 -bipyridyl-4,40 -dicarbox-
ylate)-ruthenium(II) charge-transfer sensitizers (X ¼ Cl, Br, I, CN, and SCN) on
nanocrystalline titanium dioxide electrodes. J Am Chem Soc 1993;115:
6382e90.
[38] (a) Nazeeruddin MK, Pe chy P, Renouard T, Zakeeruddin SM, Humphry-
Baker R, Comte P, et al. Engineering of efficient panchromatic sensitizers for
nanocrystalline TiO2-based solar cells. J Am Chem Soc 2001;123:1613e24.
(b) Nazeeruddin MK, Zakeeruddin SM, Humphry-Baker R, Jirousek M, Liska P,
Vlachopoulos N, et al. Acid-base equilibria of (2,20 -bipyridyl-4,40 -dicarboxylic
acid)ruthenium(II) complexes and the effect of protonation on charge-transfer
sensitization of nanocrystalline titania. Inorg Chem 1999;38:6298e305.
[39] Wang Z-S, Li F-Y, Huang C-H. Photocurrent enhancement of hemicyanine dyes
containing RSO3-group through treating TiO2 films with hydrochloric acid.
J Phys Chem B 2001;105:9210e7.
[40] Thomas KRJ, Hsu Y-C, Lin JT, Lee K-M, Ho K-C, Lai C-H, et al. 2,3-Disubstituted
thiophene based organic dyes for solar cells. Chem Mater 2008;20:1830e40.
[41] (a) Van den Berg O, Jager WF, Picken SJ. 7-Dialkylamino-1-alkylquinolinium
salts: highly versatile and stable fluorescent probes. J Org Chem 2006;71:
2666e76.
(b) Granzhan A, Ihmels H, Viola G. 9-Donor-substituted acridizinium salts:
versatile environment-sensitive fluorophores for the detection of bio-
macromolecules. J Am Chem Soc 2007;129:1254e67.
[42] (a) Hagberg DP, Edvinsson T, Marinado T, Boschloo G, Hagfeldt A, Sun L.
A novel organic chromophore for dye-sensitized nanostructured solar cells.
Chem Commun 2006:2245e7.
(b) Teng C, Yang X, Yang C, Tian H, Li S, Wang X, et al. Influence of triple bonds
as p-spacer units in metal-free organic dyes for dye-sensitized solar cells.
J Phys Chem C 2010;114:11305e13.
[43] (a) Cheng HM, Hsieh WF. High-efficiency metal-free organic-dye-sensitized
solar cells with hierarchical ZnO photoelectrode. Energy Environ Sci 2010;3:
442e7.
(b) Sayama K, Tsukagoshi S, Hara K, Ohga Y, Shinpou A, Abe Y, et al. Photo-
electrochemical properties of J aggregates of benzothiazole merocyanine dyes
on a nanostructured TiO2 film. J Phys Chem B 2002;106:1363e71.
(c) Venkateswararao A, Thomas KRJ, Lee C-P, Li C-T, Ho K-C. Organic dyes
containing carbazole as donor and p-linker: optical, electrochemical, and
photovoltaic properties. ACS Appl Mater Interfaces 2014;6:2528e39.
[44] (a) Gr€atzel M. Photoelectrochemical cells. Nature 2001;414:338e44.
(b) Hagfeldt A, Gr€ atzel M. Light-induced redox reactions in nanocrystalline
systems. Chem Rev 1995;95:49e68.
[45] Yen Y-S, Hsu Y-C, Lin JT, Chang C-W, Hsu C-P, Yin D-J. Pyrrole-based organic
dyes for dye-sensitized solar cells. J Phys Chem C 2008;112:12557e67.
[46] Van de Lagemaat J, Park N-G, Frank AJ. Influence of electrical potential dis-
tribution, charge transport, and recombination on the photopotential and
photocurrent conversion efficiency of dye-sensitized nanocrystalline TiO2
Solar Cells: a study by electrical impedance and optical modulation tech-
niques. J Phys Chem B 2000;104:2044e52.
[47] (a) Kim S, Kim D, Choi H, Kang M-S, Song K, Kang SO, et al. Enhanced
photovoltaic performance and long-term stability of quasi-solid-state dye-
sensitized solar cells via molecular engineering. Chem Commun 2008:
4951e3.
(b) Ko S, Choi H, Kang M-S, Hwang H, Ji H, Kim J, et al. Silole-spaced triaryl-
amine derivatives as highly efficient organic sensitizers in dye-sensitized solar
cells (DSSCs). J Mater Chem 2010;20:2391e9.