pubs.acs.

org/joc

Organic Dyes Containing Coplanar Diphenyl-Substituted Dithienosilole

Core for Efficient Dye-Sensitized Solar Cells
Li-Yen Lin,† Chih-Hung Tsai,‡ Ken-Tsung Wong,*,† Tsung-Wei Huang,‡ Lun Hsieh,‡
Su-Hao Liu,‡ Hao-Wu Lin,‡ Chung-Chih Wu,*,‡ Shu-Hua Chou,† Shinn-Horng Chen,§
and An-I Tsai§
†
Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan, ‡Department of Electrical
Engineering, Graduate Institute of Photonics and Optoelectronics, and Graduate Institute of Electronics
Engineering, National Taiwan University, Taipei 10617, Taiwan, and §Energy Material Research Group,
Eternal Chemical Co., Ltd., Kaohsiung 821, Taiwan

kenwong@ntu.edu.tw; chungwu@cc.ee.ntu.edu.tw
Received April 19, 2010

Two new organic dyes adopting coplanar diphenyl-substituted dithienosilole as the central linkage
have been synthesized, characterized, and used as the sensitizers for dye-sensitized solar cells (DSSCs).
The best DSSC exhibited a high power conversion efficiency up to 7.6% (TP6CADTS) under AM 1.5G
irradiation, reaching ∼96% of the ruthenium dye N719-based reference cell under the same conditions.

Introduction dye,5 have achieved remarkable power conversion efficiency

of 10-11% under standard global air mass 1.5 (AM 1.5G)
Increasing energy demands and concerns about global
illumination. However, the rarity and high cost of the ruthe-
warming have encouraged scientists to develop cheap and
nium metal may limit their development for large-scale appli-
easily accessible renewable energy sources in recent years. In
cations. Consequently, many researchers have focused on
comparison with the traditional silicon-based solar cells,1
developing metal-free organic sensitizers,7-18 and some of
dye-sensitized solar cells (DSSCs) are one of the most pro-
these endeavors have achieved decent efficiencies in the past
mising next-generation photovoltaic cells due to their versa-
tile, energy-saving, and environmentally friendly nature. (6) (a) He, Z.; Wong, W.-Y.; Yu, X.; Kwok, H.-S.; Lin, Z. Inorg. Chem.
Therefore, DSSCs have attracted much attention since the 2006, 45, 10922. (b) Wong, W.-Y.; Zhou, G.-J.; Yu, X.-M.; Kwok, H.-S.;
breakthrough made by Gr€ atzel et al. in 1991.2 Several Tang, B.-Z. Adv. Funct. Mater. 2006, 16, 838. (c) Zhou, G.; Wong, W.-Y.;
Yao, B.; Xie, Z.; Wang, L. Angew. Chem., Int. Ed. 2007, 46, 1149.
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2009, 48, 2474. (b) Wiberg, J.; Marinado, T.; Hagberg, D. P.; Sun, L.;
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(2) O’Reagen, B.; Gr€atzel, M. Nature 1991, 353, 737. Shigaki, K.; Inoue, T.; Anderson, N. A.; Ai, X.; Lian, T.; Yanagida, S.
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M€uller, E.; Liska, P.; Vlachopoulos, N.; Gr€atzel, M. J. Am. Chem. Soc. H. Chem. Commun. 2001, 569. (b) Hara, K.; Kurashige, M.; Dan-oh, Y.;
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Humphry-Baker, R.; Comte, P.; Liska, P.; Cevey, L.; Costa, E.; Shklover, V.; Shinpo, A.; Suga, S.; Sayama, K.; Sugihara, H.; Arakawa, H. J. Phys. Chem.
Spiccia, L.; Deacon, G. B.; Bignozzi, C. A.; Gr€atzel, M. J. Am. Chem. Soc. B 2003, 107, 597. (d) Wang, Z. S.; Cui, Y.; Hara, K.; Dan-oh, Y.; Kasada, C.;
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4778 J. Org. Chem. 2010, 75, 4778–4785 Published on Web 06/17/2010 DOI: 10.1021/jo100762t
r 2010 American Chemical Society
Lin et al.
JOC Article
few years.10b,c,13c,14b Among them, the donor-(π-spacer)- Among various organic conjugated materials, dithienosilole
acceptor (D-π-A) system is the basic structure for design- (DTS) derivatives and dithienosilole-based polymers are promis-
ing the organic sensitizers due to their effective photoinduced ing functional organic materials that have been widely used in
intramolecular charge-transfer characteristics. Generally, organic optoelectronic devices such as light-emitting diodes,19
arylamine-based moieties, which have also been widely used field effect transistors,20 and polymer solar cells.21 However,
in materials of organic light-emitting diodes (OLEDs), are there are few reports of utilizing the DTS moiety as the con-
employed as the electron donor due to the strong electron- jugated spacer for the organic sensitizers of DSSCs. During the
donating nature.6 On the other hand, carboxylic acid, cyano- preparation of this manuscript, Wang et al. reported a sensitizer
acrylic acid, or rhodanine-3-acetic acid were introduced into named C219 incorporating dihexyl-substituted DTS and 3,4-
the (D-π-A) system as the electron acceptor as well as the ethylenedioxythiophene unit as a binary π-conjugated spacer
anchoring group to the TiO2 surface.7 Various chromophores between a lipophilic alkoxy-substituted triphenylamine electron
such as oligoene,8 coumarin,9 indoline,10 oligothiophene,11 donor and a hydrophilic cyanoacrylic acid electron acceptor,
dithienothiophene,12 thienothiophene,13 oligophenyleneviny- leading to a high efficiency of 10.0-10.3% under AM 1.5 G
lene,14 fluorene,15 spirobifluorene,16 phenoxazine,17 and tri- irradiation.22 In the meantime, Ko et al. also reported a new
phenylamine18 have been incorporated as the conjugated class of organic dyes featuring DTS units equipped with
spacer between the electron donor and electron acceptor for various substituents at the 3-position of DTS as D-A spacers
tuning the wavelength ranges, absorption capability, and and also yielding good efficiencies from 6.73% to 7.50%.23
other characteristics required for DSSCs. In this paper, we report our design, synthesis, and charac-
terization of two new organic dyes that contain a simple
triphenylamine or dihexyloxy-substituted triphenylamine moi-
(10) (a) Horiuchi, T.; Miura, H.; Sumioka, K.; Uchida, S. J. Am. Chem.
Soc. 2004, 126, 12218. (b) Ito, S.; Zakeeruddin, S. M.; Humphry-Baker, R.; ety as the electron donor and cyanoacrylic acid as the electron
Liska, P.; Charvet, R.; Comte, P.; Nazeeruddin, M. K.; Pechy, P.; Takata, acceptor. These two building blocks are bridged by diphenyl-
M.; Miura, H.; Uchida, S.; Gr€atzel, M. Adv. Mater. 2006, 18, 1202. (c) Ito, S.; substituted DTS, which serves as a coplanar π-conjugated
Miura, H.; Uchida, S.; Takata, M.; Sumioka, K.; Liska, P.; Comte, P.; Pechy,
P.; Gr€atzel, M. Chem. Commun. 2008, 5194. spacer to give two organic D-π-A dyes TPCADTS and
(11) (a) Kim, S.; Lee, J. K.; Kang, S. O.; Ko, J.; Yum, J.-H.; Fantacci, S.; TP6CADTS (Scheme 1). We adopted the simple D-π-A
De Angelis, F.; Di Censo, D.; Nazeeruddin, M. K.; Gr€atzel, M. J. Am. Chem.
Soc. 2006, 128, 16701. (b) Choi, H.; Baik, C.; Kang, S. O.; Ko, J.; Kang,
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M.-S.; Nazeeruddin, M. K.; Grt€azel, M. Angew. Chem., Int. Ed. 2008, 47, coupling between the electron donor and electron acceptor,
327. (c) Koumura, N.; Wang, Z.-S.; Mori, S.; Miyashita, M.; Suzuki, E.; resulting in a red-shifted absorption. Hence, efficient harvest-
Hara, K. J. Am. Chem. Soc. 2006, 128, 14256. (d) Wang, Z.-S.; Koumura, N.;
Cui, Y.; Takahashi, M.; Sekiguchi, H.; Mori, A.; Kubo, T.; Furube, A.; ing of sunlight can be reasonably anticipated. In addition, the
Hara, K. Chem. Mater. 2008, 20, 3993. (e) Justin Thomas, K. R.; Hsu, Y.-C.; introduction of the diphenyl-substituted DTS as the central
Lin, J. T.; Lee, K.-M.; Ho, K.-C.; Lai, C.-H.; Cheng, Y.-M.; Chou, P.-T. linkage for the organic sensitizer possesses two advantages: (1)
Chem. Mater. 2008, 20, 1830. (f) Yum, J. H.; Hagberg, D. P.; Moon, S. J.;
Karlson, K. M.; Marinado, T.; Sun, L.; Hagfeldt, A.; Nazeeruddin, M. K.; The HOMO-LUMO gap of DTS is smaller than that of 2,20 -
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Y. S.; Hsu, Y. C.; Chou, H. H.; Lin, J. T. Org. Lett. 2010, 12, 16. (h) Wang,
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Mater. 2009, 21, 2810. of silicon σ*-orbital and bithiophene π*-orbital, namely,
(12) Qin, H.; Wenger, S.; Xu, M.; Gao, F.; Jing, X.; Wang, P.; Zakeer- σ*-π* conjugation.24 The smaller band gap of DTS is highly
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J. Org. Chem. Vol. 75, No. 14, 2010 4779

JOC Article Lin et al.

SCHEME 1. Synthesis of Dyes TPCADTS and TP6CADTS

Results and Discussion

The sensitizers TPCADTS and TP6CADTS were ob-
tained in several steps by the synthetic pathways illustrated
in Scheme 1. Different from the two previously reported
DTS-containing dyes,22,23 we adopted 5,50 -bis(trimethyl-
silyl)-3,30 -diphenylsilylene-2,20 -bithiophene (1) as the start-
ing material, which was synthesized according to the pub-
lished procedures.19b Selective monobromination of 1 gave
the key intermediate 5-bromo-50 -trimethylsilyl-3,30 -diphe-
nylsilylene-2,20 -bithiophene (2) in 66% yield. Compound 2
was then desilylated with TFA to produce 5-bromo-3,30 -
diphenylsilylene-2,20 -bithiophene (3) with an isolated yield
of 98%. The Suzuki cross-coupling reaction of 3 and boronic
acids 4a26 afforded 5a in 83% yield, whereas 5b was synthe-
sized in 61% yield by Stille coupling reaction of 3 with FIGURE 1. Absorption (solid lines) and emission (dashed lines)
tributyltin-substituted compound 4b.27 The free C2-position spectra of TPCADTS (blue lines) and TP6CADTS (red lines)
of DTS core in compound 5 was subsequently converted to measured in 2-methyl-2-propanol-acetonitrile (1:1) solution
(10-5 M).
their corresponding carbaldehydes 6 by performing the
Vilsmeier-Haack reaction, affording 6a and 6b in 64%
and 78% yield, respectively. Finally, the aldehydes were con-
(26) Li, Z. H.; Wong, M. S. Org. Lett. 2006, 8, 1499. densed with cyanoacetic acid to give the target compounds
(27) Qian, G.; Dai, B.; Luo, M.; Yu, D.; Zhan, J.; Zhang, Z.; Ma, D.; TPCADTS and TP6CADTS in 85% and 86% yield, respec-
Wang, Z. Y. Chem. Mater. 2008, 20, 6208.
(28) Hao, Y.; Yang, X.; Cong, J.; Tian, H.; Hagfeldt, A.; Sun, L. Chem. tively, via Kn€
oevenagel reaction in the presence of ammo-
Commun. 2009, 4031. nium acetate.
4780 J. Org. Chem. Vol. 75, No. 14, 2010
Lin et al.
JOC Article
TABLE 1. Photophysical and Electrochemical Parameters of the Dyes
dye λabsa/nm εa/M-1 cm-1 λema/nm λabs on TiO2b/nm E0-0c/eV Eoxd/V Erede/V Eox*f/V
TPCADTS 495 44500 579 458 1.954 1.065 -0.963 -0.889
TP6CADTS 511 36900 605 470 1.865 0.875 -0.987 -0.99
a
Absorption and emission spectra were measured in 2-methyl-2-propanol-acetonitrile (1:1) solution (10-5 M). bAbsorption spectra on TiO2 were
obtained through measuring the dye adsorbed on porous TiO2 nanoparticle film (thickness: 7 μm) in 2-methyl-2-propanol-acetonitrile (1:1) solution.
c
E0-0 was estimated from the onset point of the absorption spectra. dThe oxidation potentials of the dyes were measured in DMF with 0.1 M
tetrabutylammonium hexafluorophosphate (TBAPF6) as electrolyte. eThe reduction potentials of the dyes were measured in THF with 0.1 M
tetrabutylammonium perchlorate (TBAP) as electrolyte. For footnotes d and e: working electrode: glassy carbon; reference electrode: Ag/Agþ; counter
electrode: Pt; scan rate: 100 mV/s; calibrated with ferrocene/ferrocenium (Fc/Fcþ) as an internal reference and converted to NHE by addition of 630
mV.28 fEox* = Eox - E0-0.

FIGURE 2. Absorption spectra of the dyes anchoring on the 7 μm

porous TiO2 nanoparticle film.

The UV-vis absorption and normalized emission spectra of

dyes TPCADTS (blue lines) and TP6CADTS (red lines) in FIGURE 3. Frontier molecular orbitals (HOMO and LUMO) of
TPCADTS (a) and TP6CADTS (b) calculated with DFT on the
2-methyl-2-propanol-acetonitrile (1:1) solution are depicted in B3LYP/6-31G(d) level.
Figure 1, and the corresponding data are summarized in Table 1.
The absorption spectrum of TPCADTS shows an absorption moiety, facilitating efficient photoinduced/interfacial elec-
maximum (λmax) centered at 495 nm (ε = 44500 M-1 cm-1), tron injection from excited dyes to the TiO2 electrode.
which is assigned to the π-π* transition. TP6CADTS exhibits Quasi-reversible oxidation and reduction waves (Eox and
an absorption λmax at 511 nm (ε = 36900 M-1 cm-1) that is Ered in Table 1) were observed for the dyes TPCADTS and
red-shifted by 16 nm as compared to that of TPCADTS due to TP6CADTS in the cyclic voltammetry (CV) measurements
the stronger electron-donating nature of hexyloxy substitu- (Figure 4). The oxidation can be attributed to the tripheny-
ents. TPCADTS and TP6CADTS exhibit emission bands lamine moieties, while the reduction can be assigned to the
centered at 579 and 605 nm, respectively, as excited on their cyanoacrylic acid. Both oxidation and reduction potentials
absorption maxima. Upon anchoring on the 7 μm porous of TP6CADTS are more negative than those of TPCADTS,
TiO2 nanoparticle film, the absorption maxima of these two yet the difference in reduction potentials of the two dyes is
dyes show blue-shifted behavior (Figure 2) in comparison with smaller than that in oxidation potentials. It suggests that the
those in 2-methyl-2-propanol-acetonitrile (1:1) solution. The introduction of a hexyloxy substituent on the triphenylamine
blue shift is attributed to the deprotonation of carboxylic acid moiety has a significant influence on the ground-state oxida-
upon adsorption onto the TiO2 surface, and the resulting tion potential but a more limited effect on the ground-state
carboxylate-TiO2 unit is a weaker electron acceptor com- reduction potential of TP6CADTS. The different influence
pared to the carboxylic acid.29 on the ground-state oxidation and reduction potential by
To gain more insight into the electronic structures of incorporating the stronger donor leads to a narrow energy
TPCADTS and TP6CADTS, density function theory (DFT) gap of TP6CADTS. The zero-zero excitation energy (E0-0)
calculations were performed at a B3LYP/6-31G(d) level for estimated from the absorption onset and the ground-state
the geometry optimization. As shown in Figure 3, the HOMOs oxidation potential (Eox) were used to calculate the excited-
of both sensitizers are mainly populated over the triphenyla- state oxidation potential (Eox*). The deduced Eox* values of
mine and dithienosilole blocks with considerable contribution these two dyes are more negative than the conduction band
from the former, whereas LUMOs are delocalized through edge of the TiO2 (-0.5 V vs NHE),30 indicating that the
the dithienosilole and cyanoacrylic acid fragments with electron injection process shall be energetically favorable. On
sizable contribution from the latter. Examination of the the other hand, the ground-state oxidation potentials (Eox in
frontier orbitals of both sensitizers suggests that the HOMO- Table 1) of these two dyes are more positive than the redox
LUMO excitation would shift the electron density distri- potential of the iodide/triiodide couple (0.4 V vs NHE). It
bution from the triphenylamine unit to the cyanoacrylic acid suggests that the oxidized dyes shall be able to accept

(29) Wang, Z.-S.; Cui, Y.; Dan-oh, Y.; Kasada, C.; Shinpo, A.; Hara, K. (30) Klein, C.; Nazeeruddin, M. K.; Censo, D. D.; Liska, P.; Gr€
atzel, M.
J. Phys. Chem. C 2007, 111, 7224. Inorg. Chem. 2004, 43, 4216.

J. Org. Chem. Vol. 75, No. 14, 2010 4781

JOC Article Lin et al.

FIGURE 4. Cyclic voltammograms of TPCADTS (blue lines) and FIGURE 5. IPCE spectra of DSSCs based on TPCADTS and
TP6CADTS (red lines); 0.1 M TBAP (reduction) in THF and 0.1 M TP6CADTS.
TBAPF6 (oxidation) in DMF were used as supporting electrolytes.
A glassy carbon electrode was used as the working electrode; scan
rate: 100 mV/s.

electrons from I- thermodynamically for effective dye re-

generation and to avoid the charge recombination process
between oxidized dyes and photoinjected electrons in the
TiO2 film.
The photovoltaic characteristics of TPCADTS and
TP6CADTS as the sensitizers in DSSCs were evaluated with
a sandwich DSSC cell comprising 0.6 M 1-butyl-3-methyli-
midazolium iodide (BMII), 0.05 M LiI, 0.03 M I2, 0.5 M
4-tert-butylpyridine, and 0.1 M guanidinium thiocyanate in
a mixture of acetonitrile-valeronitrile (85: 15, v/v) as the
redox electrolyte. Details of the device preparation and
characterization are described in the Experimental Section.
It was reported that the incorporation of 4-tert-butylpyri-
FIGURE 6. Photocurrent density vs voltage for DSSCs based on
dine can decrease the dark current and shift the conduction TPCADTS and TP6CADTS under AM 1.5 G simulated solar light
band edge of the TiO2 to a more negative potential. As a (100 mW cm-2).
result, the open-circuit voltage and fill factor can be im-
proved, leading to an improvement on overall conversion η value of 6.65% (see Table 2). For a fair comparison, the
efficiencies.31 The incident monochromatic photon-to-cur- N719-sensitized DSSC was also fabricated under the same
rent conversion efficiency (IPCE) spectra of the DSSCs are conditions. The efficiency of the TP6CADTS-based cell reaches
shown in Figure 5. The IPCE spectrum of TP6CADTS is ∼96% of the N719 cell efficiency (7.93%). The higher Jsc value
broader than that of TPCADTS, as can be expected from the of the TP6CADTS-based cell than that of the TPCADTS-
absorption spectrum of TP6CADTS anchoring on the 7 μm based cell is consistent with the values for the IPCE spectra,
porous TiO2 film or its absorption in solutions. The IPCE of reflecting the better sunlight-harvesting ability of TP6CADTS.
TP6CADTS exceeds 70% from 350 to 560 nm and reaches a The two hexyloxy chains of TP6CADTS may also contribute to
maximum of 84% at 450 nm. Among these two sensitizer dyes, inhibition of dye aggregation and thus to enhancement of Jsc.13a
TP6CADTS shows higher peak IPCE, although its maximal In addition, with the existence of two aliphatic hexyloxy chains,
absorption coefficient may not necessarily be higher than that one also notes that the TP6CADTS-based cell gives a 50 mV
of TPCADTS. The higher peak IPCE of TP6CADTS than increase in Voc in comparison with the TPCADTS-based cell.
that of TPCADTS may be ascribed to the reduced charge The effects of the two longer hexyloxy chains on photo-
recombination at the TiO2/dye/electrolyte interface by tailor- voltaic characteristics were further elucidated by electroche-
ing with two longer aliphatic hexyloxy chains.13a mical impedance spectroscopy (EIS). The EIS is a useful tool
Figure 6 shows the current-voltage (J-V) curves of the for characterizing important interfacial charge-transfer pro-
DSSCs under standard global AM 1.5G solar irradiation. cesses in DSSCs, such as the charge recombination at the
The short-circuit photocurrent density (Jsc), open-circuit TiO2/dye/electrolyte interface, electron transport in the
voltage (Voc), and fill factor (ff) of the solar cell based on TiO2 electrode, electron transfer at the counter electrode,
TP6CADTS are 13.39 mA cm-2, 0.81 V, and 0.70, respec- and I3- transport in the electrolyte etc.32-34 In this study, the
tively, yielding an overall conversion efficiency (η) of 7.60%.
Under the same conditions, the device based on TPCADTS (32) Andrade, L.; Zakeeruddin, S. M.; Nazeeruddin, M. K.; Ribeiro,
shows relatively lower Jsc and Voc, leading to an inferior H. A.; Mendes, A.; Gr€atzel, M. ChemPhysChem 2009, 10, 1117.
(33) Zhang, J.; Yang, G.; Sun, Q.; Zheng, J.; Wang, P.; Zhu, Y.; Zhao, X.
J. Renewable Sustainable Energy 2 2010, 013104.
(31) (a) Hara, K.; Dan-oh, Y.; Kasada, C.; Ohga, Y.; Shinpo, A.; Suga, S.; (34) Fabregat-Santiago, F.; Bisquert, J.; Palomares, E.; Otero, L.;
Sayama, K.; Arakawa, H. Langmuir 2004, 20, 4205. (b) Boschloo, G.; Kuang, D.; Zakeeruddin, S. M.; Gra1tzel, M. J. Phys. Chem. C 2007, 111,
H€aggman, L.; Hagfeldt, A. J. Phys. Chem. B 2006, 110, 13144. 6550.

4782 J. Org. Chem. Vol. 75, No. 14, 2010

Lin et al.
JOC Article
TABLE 2. DSSC Performance Parameters of the Dyesa
dye Jsc/mA cm-2 Voc/V ff η (%)
TPCADTS 12.70 0.76 0.69 6.65
TP6CADTS 13.39 0.81 0.70 7.60
N719 14.65 0.77 0.70 7.93
a
The concentration of the dyes was maintained at 0.5 mM in
2-methyl-2-propanol-acetonitrile (1:1, v/v) solution, with 0.5 mM
deoxycholic acid (DCA) as a co-adsorbent. Performances of DSSCs
were measured with a 0.125 cm2 working area. Irradiating light: AM
1.5 G (100 mW cm-2).

FIGURE 8. EIS Bode plots (i.e., the phase of the impedance vs the
frequency) for DSSCs based on TPCADTS and TP6CADTS dyes.

related to the charge recombination rate, and its reciprocal is

associated with the electron lifetime.35,36 As can be seen in
Figure 8, the lower frequency peak of the TP6CADTS cell
shifts to a lower frequency (compared to the TPCADTS cell),
indicating that the electron lifetime was effectively prolonged
by the two longer hexyloxy chains near the TiO2/dye/electro-
lyte interface. EIS results of Figures 7 and 8 clearly suggest
that the two longer hexyloxy chains of TP6CADTS act as
FIGURE 7. EIS Nyquist plots (i.e., minus imaginary part of the effective blocking units between TiO2 surface and electrolyte,
impedance -Z00 vs the real part of the impedance Z0 when sweeping preventing hydrophilic I3- ions approaching the TiO2 surface
the frequency) for DSSCs based on TPCADTS and TP6CADTS dyes. and thereby leading to suppressed charge recombination/dark
current and lengthened electron lifetimes.11c,d,37 These factors
impedance spectroscopy was carried out by subjecting the may in turn lead to the higher Voc (50 mV higher) of the
cell to the constant AM 1.5G 100 mW/cm2 illumination and TP6CADTS cell than that of the TPCADTS cell.
to the bias at the open-circuit voltage Voc of the cell (namely,
under the conditions of no dc electric current),34 for better Conclusions
manifesting the process at the TiO2/electrolyte interface of
a cell under operation. Figure 7 shows the EIS Nyquist plots In summary, we had successfully designed and synthesized
(i.e., minus imaginary part of the impedance -Z00 vs the real two new organic sensitizers (TPCADTS and TP6CADTS)
part of the impedance Z0 when sweeping the frequency) for containing coplanar diphenyl-substituted dithienosilole as the
DSSCs based on TPCADTS and TP6CADTS dyes. For the central linkage for high-performance dye-sensitized solar cells.
frequency range investigated (20 Hz to 1 MHz), in both cells, By incorporating the diphenyl-substituted DTS core, these
a larger semicircle occurs in the lower frequency range (∼20 Hz two dyes exhibited the enhanced light-capturing abilities and
to 1 kHz) and a smaller semicircle occurs in the higher fre- suppressed dye aggregation. These two dyes had been em-
quency range. With the bias illumination and voltage applied, ployed as the organic sensitizers in DSSCs. A solar-cell device
the larger semicircle at lower frequencies corresponds to the based on the sensitizer TP6CADTS yielded a higher overall
charge-transfer processes at the TiO2/dye/electrolyte inter- conversion efficiency up to 7.6%, reaching ∼96% of the ruthe-
face, while the smaller semicircle at higher frequencies corres- nium dye N719-based reference cell under the same condi-
ponds to the charge-transfer processes at the Pt/electrolyte tions. The introduction of aliphatic hexyloxy chains on the
interface. The two cells hardly show a difference in smaller donor (e.g., TP6CADTS) appears to be beneficial to suppres-
semicircles at higher frequencies, but the difference in larger sion of electronic coupling and charge recombination, etc. at
semicircles at lower frequencies is significant. The larger width the TiO2/dye/electrolyte interface, which could contribute to
of the lower frequency semicircle of the TP6CADTS cell higher Voc and IPCE in DSSCs. The results disclosed in this
indicates a larger charge-transfer resistance at the TiO2/dye/ paper are believed to be useful for further development of
electrolyte interface. other low-cost metal-free organic dyes by different molecular
Figure 8 shows the EIS Bode plots (i.e., the phase of the and energy-level engineering processes.
impedance vs the frequency) of the DSSCs based on TPCADTS
and TP6CADTS dyes. For the frequency range investigated, Experimental Section
both EIS Bode plots also exhibit two peak features; the one at Synthesis of the Dyes. General Methods. All chemicals and
higher frequencies corresponds to the charge transfer at the reagents were used as received from commercial sources without
Pt/electrolyte interface and the one at lower frequencies corres-
ponds to the charge transfer at the TiO2/dye/electrolyte inter- (35) Adachi, M.; Sakamoto, M.; Jiu, J.; Ogata, Y.; Isoda, S. J. Phys.
face. Again, the difference in bode plots of both cells mainly Chem. B 2006, 110, 13872.
(36) Wang, Q.; Moser, J.; Gr€atzel, M. J. Phys. Chem. B 2005, 109, 14945.
occurs in the lower frequency range. The characteristic (37) Kim, S.; Kim, D.; Choi, H.; Kang, M. S.; Song, K.; Kang, S. O.; Ko,
frequency of the lower frequency peak in the Bode plot is J. Chem. Commun. 2008, 4951.

J. Org. Chem. Vol. 75, No. 14, 2010 4783

JOC Article Lin et al.

purification. Solvents for chemical synthesis were purified by 6.99 (d, J = 8.8 Hz, 4H), 6.87 (d, J = 8.8 Hz, 4H), 6.75 (d, J =
distillation. All chemical reactions were carried out under an 8.4 Hz, 2H), 3.89 (t, J = 6.2 Hz, 4H), 1.67 (m, 4H), 1.38 (m, 4H),
argon or nitrogen atmosphere. 1.29 (m, 8H), 0.86 (t, J = 6.2 Hz, 6H); 13C NMR (CD2Cl2, 100 MHz)
5-Bromo-50 -trimethylsilyl-3,30 -diphenylsilylene-2,20 -bithiophene δ 156.1, 151.0, 148.7, 148.2, 146.8, 141.6, 140.6, 139.3, 135.7, 132.2,
(2). To a stirring solution of 1 (13.55 g, 27.60 mmol) in N,N- 130.7, 130.0, 128.6, 127.2, 126.6, 126.4, 126.3, 124.4, 120.4, 115.7,
dimethylformamide (275 mL) was dropwise added N-bromosucci- 68.8, 32.2, 29.9, 26.4, 23.3, 14.5; HRMS (m/z, FABþ) calcd for
nimide (5.86 g, 33.12 mmol) in N,N-dimethylformamide (275 mL) C50H51NO2S2Si 789.3130, found 789.3133.
at 0 °C under exclusion of light, and the reaction mixture was then 5-[N,N-Bis(phenylamino)phenyl]-50 -formyl-3,30 -diphenylsilylene-
warmed to room temperature. After being stirred for 12 h, the re- 2,20 -bithiophene (6a). To a stirring solution of 5a (826 mg, 1.4
action mixture was poured into water and extracted with diethyl mmol) in dry N,N-dimethylformamide (30 mL) was dropwise
ether, and the combined extracts were washed with brine, dried added phosphorus oxychloride (0.22 mL, 2.38 mmol) at -40 °C
over anhydrous magnesium sulfate, and filtered. The solvent was under argon. The reaction mixture was then heated to 60 °C and
removed by rotary evaporation. The crude product was dissolved stirred for 4 h. After being cooled to room temperature, the
in hexane, and the undissolved solid was filtered. The filtrate was reaction mixture was quenched with 10% sodium acetate aqueous
evaporated to dryness, and the resulting solid was washed with solution (210 mL) and extracted with ethyl acetate, and the
ethanol to afford 2 as a white solid (9.04 g, 66% yield): mp combined extracts were washed with brine, dried over anhydrous
140-142 °C; IR (KBr) ν 3065, 2950, 1587, 1427, 1245, 995 cm-1; magnesium sulfate, and filtered. The solvent was removed by
1
H NMR (CDCl3, 400 MHz) δ 7.63 (dt, J = 6.4, 1.6 Hz, 4H), rotary evaporation, and the crude product was purified by column
7.45-7.36 (m, 6H), 7.31 (s, 1H), 7.18 (s, 1H), 0.36 (s, 9H); 13C chromatography on silica gel with ethyl acetate/hexane (v/v, 1:10)
NMR (CDCl3, 100 MHz) δ 154.8, 150.6, 142.5, 140.3, 136.1, as eluent to afford 6a as a red solid (553 mg, 64% yield): mp
135.2, 132.1, 131.1, 130.3, 128.1, 111.9, 0.3; HRMS (m/z, FABþ) 235-237 °C; IR (KBr) ν 3031, 2809, 1657, 1589, 1487, 1115, 825
calcd for C23H21BrS2Si2 495.9807, found 495.9803. cm-1; 1H NMR (CDCl3, 400 MHz) δ 9.87 (s, 1H), 7.86 (s, 1H),
5-Bromo-3,30 -diphenylsilylene-2,20 -bithiophene (3). To a stir- 7.65 (dd, J = 8.0, 1.2 Hz, 4H), 7.49-7.45 (m, 4H), 7.41-7.37 (m,
ring solution of 2 (3.30 g, 6.63 mmol) in chloroform (165 mL) 5H), 7.30-7.26 (m, 4H), 7.12 (dd, J = 8.4, 0.8 Hz, 4H), 7.08-7.04
was dropwise added trifluoroacetic acid (0.98 mL, 13.26 mmol) (m, 4H); 13C NMR (CDCl3, 100 MHz) δ 182.2, 159.7, 149.9, 147.8,
at room temperature under exclusion of light. After being stirred 147.1, 146.7, 145.8, 144.7, 139.9, 139.4, 135.2, 130.7, 130.2, 129.2,
for 12 h, the reaction mixture was poured into water and extrac- 128.3, 127.3, 126.7, 124.9, 124.6, 123.3, 123.1; HRMS (m/z, FABþ)
ted with chloroform, and the combined extracts were washed calcd for C39H27NOS2Si 617.1303, found 617.1304.
with brine, dried over anhydrous magnesium sulfate, and fil- 5-[N,N-Bis(4-hexyloxyphenylamino)phenyl]-50 -formyl-3,30 -di-
tered. The solvent was removed by rotary evaporation to afford phenylsilylene-2,20 -bithiophene (6b). To a stirring solution of 5b
3 as a light yellow solid (2.75 g, 98% yield): mp 173-175 °C; IR (2 g, 2.53 mmol) in dry N,N-dimethylformamide (54 mL) was
(KBr) ν 3090, 3018, 1586, 1427, 1250, 943 cm-1; 1H NMR dropwise added phosphorus oxychloride (0.4 mL, 4.3 mmol) at
(CDCl3, 400 MHz) δ 7.64 (d, J = 6.8 Hz, 4H), 7.47-7.37 (m, -40 °C under argon. The reaction mixture was then heated to
6H), 7.30 (d, J = 4.8 Hz, 1H), 7.24 (d, J = 4.8 Hz, 1H), 7.20 (s, 60 °C and stirred for 3 h. After being cooled to room temperature,
1H); 13C NMR (CDCl3, 100 MHz) δ 150.5, 149.6, 139.9, 138.7, the reaction mixture was quenched with 10% sodium acetate
135.2, 132.0, 130.9, 130.4, 129.5, 128.1, 126.2, 111.8; HRMS (m/z, aqueous solution (380 mL) and extracted with ethyl acetate, and
FABþ) calcd for C20H13BrS2Si 423.9411, found 423.9416. the combined extracts were washed with brine, dried over anhy-
5-[N,N-Bis(phenylamino)phenyl]-3,30 -diphenylsilylene-2,20 - drous magnesium sulfate, and filtered. The solvent was removed
bithiophene (5a). A mixture of 3 (2.33 g, 5.48 mmol), 4a (1.90 g, by rotary evaporation, and the crude product was purified by
6.58 mmol), tetrakis(triphenylphosphine)palladium(0) (316 mg, column chromatography on silica gel with ethyl acetate/hexane (v/
0.27 mmol), and potassium carbonate (2 M aqueous solution, v, 1:10) as eluent to afford 6b as a red solid (1.62 g, 78% yield): mp
13.7 mL, 27.40 mmol) in toluene (270 mL) was stirred and heated 65-67 °C; IR (KBr) ν 3061, 2953, 2856, 2706, 1664, 1599, 1506,
to reflux under argon for 2.5 h. The reaction mixture was poured 1237, 1139, 825 cm-1; 1H NMR (DMSO-d6, 400 MHz) δ 9.87 (s,
into water and extracted with dichloromethane, and the com- 1H), 8.40 (s, 1H), 7.86 (s, 1H), 7.70 (d, J = 7.2 Hz, 4H), 7.55-7.41
bined extracts were washed with brine, dried over anhydrous (m, 8H), 7.03 (d, J = 8.8 Hz, 4H), 6.90 (d, J = 8.8 Hz, 4H), 6.74 (d,
magnesium sulfate, and filtered. The solvent was removed by J = 8.4 Hz, 2H), 3.92 (t, J = 6.8 Hz, 4H), 1.69 (m, 4H), 1.39 (m,
rotary evaporation, and the crude product was purified by 4H), 1.30 (m, 8H), 0.87 (t, J = 6.8 Hz, 6H); 13C NMR (CD2Cl2,
column chromatography on silica gel with dichloromethane/ 100 MHz) δ 182.6, 159.9, 156.4, 150.9, 149.4, 146.5, 146.4, 145.2,
hexane (v/v, 1:5) as eluent to afford 5a as a yellow solid (2.68 g, 140.3, 140.2, 139.8, 135.7, 131.1, 130.9, 128.7, 127.5, 126.9, 125.5,
83% yield): mp 230-232 °C; IR (KBr) ν 3059, 3023, 1590, 1494, 124.7, 119.9, 115.7, 68.8, 32.2, 29.9, 26.3, 23.3, 14.5; HRMS (m/z,
1273, 826 cm-1; 1H NMR (CDCl3, 400 MHz) δ 7.67 (dt, J = 6.4, FABþ) calcd for C51H51NO3S2Si 817.3080, found 817.3077.
1.6 Hz, 4H), 7.48-7.22 (m, 15 H), 7.12 (dd, J = 8.4, 1.2 Hz, 4H), 3-[5-[N,N-Bis(phenylamino)phenyl]-3,30 -diphenylsilylene-2,20 -
7.07-7.02 (m, 4H); 13C NMR (CDCl3, 100 MHz) δ 150.5, 148.4, bithiophene-50 -yl]-2-cyanoacrylic Acid (TPCADTS). A mixture
147.3, 146.9, 145.7, 141.1, 139.0, 135.3, 131.6, 130.2, 129.5, 129.2, of 6a (370 mg, 0.6 mmol), cyanoacetic acid (153 mg, 1.8 mmol),
128.4, 128.1, 126.3, 125.8, 124.6, 124.3, 123.6, 122.9; HRMS (m/z, and ammonium acetate (39 mg) in glacial acetic acid (13 mL)
FABþ) calcd for C38H27NS2Si 589.1354, found 589.1349. was stirred and heated at 120 °C for 12 h. After the mixture was
5-[N,N-Bis(4-hexyloxyphenylamino)phenyl]-3,30 -diphenylsily- cooled to room temperature, the resulting precipitate was collec-
lene-2,20 -bithiophene (5b). A mixture of 3 (2.94 g, 6.91 mmol), 4b ted by filtration and thoroughly washed with water, methanol,
(7.61 g, 10.37 mmol), tetrakis(triphenylphosphine)palladium(0) and diethyl ether to afford TPCADTS as a black solid (350 mg,
(404 mg, 0.35 mmol) in toluene (35 mL) was stirred and heated at 85% yield): mp 294-296 °C; IR (KBr) ν 3056, 2217, 1718, 1682,
100 °C under argon for 24 h. After the mixture was cooled to 1592, 1429, 824 cm-1; 1H NMR (DMSO-d6, 400 MHz) δ 8.46 (s,
room temperature, the solvent was removed by rotary evapora- 1H), 8.32 (s, 1H), 7.96 (s, 1H), 7.69-7.64 (m, 6H), 7.52-7.48 (m,
tion, and the crude product was purified by column chromato- 2H), 7.46-7.42 (m, 4H), 7.35-7.31 (m, 4H), 7.11-7.05 (m, 6H),
graphy on silica gel with dichloromethane/hexane (v/v, 1:3) as 6.97 (d, J = 8.8 Hz, 2H); 13C NMR (DMSO-d6, 100 MHz) δ
eluent to afford 5b as a yellow solid (3.32 g, 61% yield): mp 163.8, 158.8, 149.8, 147.5, 146.6, 146.4, 145.5, 143.4, 139.8,
55-57 °C; IR (KBr) ν 3063, 2955, 2853, 1601, 1505, 1475, 1011, 137.3, 135.0, 130.9, 129.9, 129.7, 128.5, 126.9, 126.6, 126.3,
824 cm-1; 1H NMR (DMSO-d6, 400 MHz) δ 7.71 (s, 1H), 7.66 124.6, 123.7, 122.5, 116.9; HRMS (m/z, FABþ) calcd for
(d, J = 6.8 Hz, 4H), 7.56 (d, J = 4.4 Hz, 1H), 7.50-7.37 (m, 9H), C42H28N2O2S2Si 684.1361, found 684.1357.

4784 J. Org. Chem. Vol. 75, No. 14, 2010

Lin et al.
JOC Article
3-[5-[N,N-Bis(4-hexyloxyphenylamino)phenyl]-3,30 -diphenylsily- dye-adsorbed TiO2 working electrode and a counter electrode
lene-2,20 -bithiophene-50 -yl]-2-cyanoacrylic Acid (TP6CADTS). A were then assembled into a sealed DSSC cell with a sealant spacer
mixture of 6b (327 mg, 0.4 mmol), cyanoacetic acid (102 mg, 1.2 between the two electrode plates. A drop of electrolyte solution
mmol), and ammonium acetate (26 mg) in glacial acetic acid (9 mL) [0.6 M 1-butyl-3-methylimidazolium iodide (BMII), 0.05 M LiI,
was stirred and heated at 120 °C for 12 h. After being cooled to 0.03 M I2, 0.5 M 4-tert-butylpyridine, and 0.1 M guanidinium
room temperature, the resulting precipitate was collected by filtra- thiocyanate in a mixture of acetonitrile-valeronitrile (85:15, v/v)]
tion and thoroughly washed with water, methanol, and hexane to was injected into the cell through a drilled hole. Finally, the hole
afford TP6CADTS as a black solid (305 mg, 86% yield): mp was sealed using the sealant and a cover glass. A mask with an
244-246 °C; IR (KBr) ν 3062, 2930, 2854, 2215, 1719, 1682, 1565, aperture area of 0.125 cm2 was covered on a testing cell during
1373, 822 cm-1; 1H NMR (DMSO-d6, 400 MHz) δ 8.46 (s, 1H), photocurrent-voltage and incident photon-to-current conver-
8.31 (s, 1H), 7.87 (s, 1H), 7.67 (d, J = 7.2 Hz, 4H), 7.56-7.42 (m, sion efficiency measurements.
8H), 7.03 (d, J = 8.8 Hz, 4H), 6.90 (d, J = 8.8 Hz, 4H), 6.75 (d, J = Photocurrent-Voltage Measurement. The photocurrent-
8.4 Hz, 2H), 3.92 (t, J = 6.8 Hz, 4H), 1.69 (m, 4H), 1.40 (m, voltage characteristics of the DSSCs were measured under
4H), 1.30 (m, 8H), 0.88 (t, J = 6.8 Hz, 6H); 13C NMR (DMSO-d6, illumination of AM1.5G solar light from a 300-W xenon lamp
100 MHz) δ 164.5, 156.3, 151.2, 149.4, 147.2, 145.5, 140.3, 139.9, solar simulator. The incident light intensity was calibrated as
137.8, 135.7, 131.6, 130.7, 129.2, 127.8, 127.4, 126.2, 124.9, 119.3, 100 mW/cm2. Photocurrent-voltage curves were obtained by
116.2, 68.3, 31.7, 29.4, 25.9, 22.7, 14.6; HRMS (m/z, FABþ) calcd applying an external bias voltage to the cell and measuring the
for C54H52N2O4S2Si 884.3138, found 884.3146. generated photocurrent.
Theoretical Calculation. Density functional theory (DFT) Incident Monochromatic Photon-to-Current Conversion Effi-
calculations were conducted by using the B3LYP hybrid func- ciency Measurement. The incident monochromatic photon-to-
tional for the geometry optimizations. The molecular orbital current conversion efficiency (IPCE) spectra were measured by
levels of HOMO and LUMO were achieved with the 6-31G(d) using a 75-W xenon lamp as the light source coupled to a
basis set implemented in the Gaussian 03 package. monochromator.38 The IPCE data were taken by illuminating
Measurement of Absorption Spectra of Dye-Loaded Nanoporous monochromatic light on the solar cells (with a wavelength
TiO2 Films. A 7 μm thick transparent porous TiO2 nanoparticle sampling interval of 10 nm from 350 to 700 nm) and measuring
layer (adopting 20 nm anatase TiO2 nanoparticles) was coated on the short-circuit current of the solar cells. The IPCE measure-
a glass plate by the doctor-blade method. After being sintered at ment was performed with a lock-in amplifier, a low-peed
500 °C for 30 min, the TiO2 film was immersed into the dye chopper, and a bias light source under full computer control.
solutions of 0.5 mM dye in acetonitrile and 2-methyl-2-propanol Electrochemical Impedance Spectroscopy Measurement. The
(volume ratio 1:1) at room temperature for 24 h. The UV-vis electrochemical impedance spectroscopy (EIS) of the cells was
absorption spectrum of the dye-loaded TiO2 film was then measured by using an impedance analyzer with a frequency
recorded on a spectrophotometer. range of 20 Hz to 1 MHz. In this study, during the impedance
Fabrication of Dye-Sensitized Solar Cells. To prepare the measurement, the cell was under the constant AM 1.5G 100 mW/
DSSC working electrodes, the FTO glass plates were first cm2 illumination. The impedance of the cell (throughout the
cleaned in a detergent solution using an ultrasonic bath for 15 frequency range of 20 Hz to 1 MHz) was then measured by
min and then rinsed with water and ethanol. A layer of 20 nm applying a bias at the open-circuit voltage Voc of the cell (namely,
anatase TiO2 nanoparticles for the transparent nanocrystalline under the condition of no dc electric current) and by using an ac
layer was first coated on the FTO glass plates by the doctor- amplitude of 10 mV.
blade method. After the film was dried at 120 °C, another layer
of 400 nm anatase TiO2 nanoparticles was then deposited as the Acknowledgment. This work was financially supported by
light-scattering layer of the DSSC. The resulting working elec-
trode was composed of a 7 μm thick transparent TiO2 nano- the National Science Council of Taiwan.
particle layer (particle size: 20 nm) and a 5 μm thick TiO2
scattering layer (particle size: 400 nm). The nanoporous TiO2 Supporting Information Available: 1H and 13C NMR spec-
electrodes were then sequentially heated at 150 °C for 10 min, tra for all new compounds. This material is available free of
at 300 °C for 10 min, at 400 °C for 10 min, and finally, at 500 °C charge via the Internet at http://pubs.acs.org.
for 30 min. After cooling, the nanoporous TiO2 electrodes were
immersed into the dye solutions of 0.5 mM dye and 0.5 mM (38) (a) Lin, H.-W.; Ku, S.-Y.; Su, H.-C.; Huang, C.-W.; Lin, Y.-T.; Wong,
deoxycholic acid (DCA) in acetonitrile and 2-methyl-2-propanol K.-T.; Wu, C.-C. Adv. Mater. 2005, 17, 2489. (b) Yang, C.-J.; Cho, T.-Y.; Lin,
C.-L.; Wu, C.-C. Appl. Phys. Lett. 2007, 90 (17), 173507. (c) Yang, C.-Y.; Cho,
(volume ratio 1:1) at room temperature for 24 h. Counterelec- T.-Y.; Chen, Y.-Y.; Yang, C.-J.; Meng, C.-Y.; Yang, C.-H.; Yang, P.-C.; Wu,
trodes of the DSSC were prepared by depositing 40 nm thick C.-C.; Lee, S.-C. Appl. Phys. Lett. 2007, 90 (23), 233512. (d) Yang, C.-J.; Cho,
Pt films on the FTO glass plates by e-beam evaporation. The T.-Y.; Lin, C.-L.; Wu, C.-C. J. Soc. Inf. Display 2008, 16 (6), 691.

J. Org. Chem. Vol. 75, No. 14, 2010 4785