Accepted Manuscript

Dithienopyrrolobenzotriazole-based organic dyes with high molar extinction coefficient

for efficient dye-sensitized solar cells

Zu-Sheng Huang, Tao Hua, Jing Tian, Lingyun Wang, Herbert Meier, Derong Cao

PII: S0143-7208(15)00405-2
DOI: 10.1016/j.dyepig.2015.10.022
Reference: DYPI 4969

To appear in: Dyes and Pigments

Received Date: 25 September 2015

Revised Date: 20 October 2015
Accepted Date: 22 October 2015

Please cite this article as: Huang Z-S, Hua T, Tian J, Wang L, Meier H, Cao D,
Dithienopyrrolobenzotriazole-based organic dyes with high molar extinction coefficient for efficient dye-
sensitized solar cells, Dyes and Pigments (2015), doi: 10.1016/j.dyepig.2015.10.022.

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 ACCEPTED MANUSCRIPT

Dithienopyrrolobenzotriazole-based organic dyes

with high molar extinction coefficient for efficient
dye-sensitized solar cells
Zu-Sheng Huanga, Tao Huaa, Jing Tiana, Lingyun Wanga, Herbert Meierb, Derong

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Caoa,*

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School of Chemistry and Chemical Engineering, State Key Laboratory of

Luminescent Materials Devices, South China University of Technology, Guangzhou

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510641, China.

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b
Institute of Organic Chemistry, University of Mainz, Mainz 55099, Germany.
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* Corresponding Author: Cao, D. Tel.: +86-20-87110245. Fax: +86-20-87110245.

Email: drcao@scut.edu.cn
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ABSTRACT

Four novel organic dyes DT1-DT4 containing a dithienopyrrolobenzotriazole unit

were synthesized and applied in dye sensitized solar cells, where

dithienopyrrolobenzotriazole moiety was introduced as a π-spacer for the first time.

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The four dyes exhibited good light harvesting efficiency with high molar extinction

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coefficients and broad spectral response. The influence of the different electron donor

on the photovoltaic performance was evaluated. The effects of the linear and branched

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alkyl chains in the π-bridge on the photophysical, electrochemical and photovoltaic

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performance were systemically investigated. The results show that branched alkyl
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chains are better than linear alkyl chains in inhibition of intermolecular aggregation

and electron recombination between the injection electrons and electrolyte. Finally,
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DT4 sensitized solar cell obtained a power conversion efficiency of 8.05%. These
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results indicate that the dithienopyrrolobenzotriazole-based organic sensitizer is a

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promising candidate for efficient dye sensitized solar cells.

Keywords: organic dyes; dithienopyrrolobenzotriazole; dye-sensitized solar cells;

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electron donors; alkyl chains; photovoltaic performance

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1. Introduction
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In the past two decades, dye-sensitized solar cells (DSSCs) have attracted

considerable scientific research attention as a promising candidate for the next

generation of solar cells due to their easy fabrication, low cost and high power

conversion efficiency (PCE) [1,2]. In DSSCs, the sensitizer plays a crucial role in

light-harvesting and electron injection, which greatly influences the photovoltaic

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performance of the solar cells. Presently, sensitizers can be divided into three main

categories: ruthenium (Ru) complexes dyes, zinc-porphyrin based sensitizers and

metal-free organic dyes. The Ru-complexes based solar cells have obtained high PCE

over 11% [3-5] and Zn-porphyrin based DSSCs have reached the efficiency up to 13%

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[6-9]. However, the use of rare and high-cost ruthenium limits the Ru-complexes

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sensitizers’ practical application. On the other hand, the low yield, multiple synthetic

steps as well as difficult purification procedure might limit application of

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Zn-porphyrin dyes.

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Recently, metal-free organic dyes based devices have achieved a very competitive
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PCE about 12.5% with the other two types of sensitizers [10]. Moreover, their

distinctly advantages such as low cost, high molar extinction coefficients and easy
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structural modification are conducive to the commercial application. Up to date, the

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commonly designed configuration of metal-free organic dyes are

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donor-π-bridge-acceptor (D-π-A) architecture which show efficient intramolecular

charge transfer (ICT) properties [11-13]. Apart from the electron donor and electron
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acceptor in the D-π-A structure, the π-bridge is of great importance in tuning the
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energy gap and absorption properties of the dye molecule, which would significantly
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affect the DSSCs performance. In particular, the geometry of the dye molecule should

be relatively planar, which can facilitate the electron migration from the donor to the

acceptor [2]. Some successful molecular engineering for high DSSCs performances

have been achieved by incorporating planar units into the π-linker, such as

cyclopentadithiophene[14,15], naphtho[2,1-b:3,4-b’]dithiophene[16,17], dithieno-

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[3,2-b:2',3'-d]pyrrole [18-20], dithieno[2,3-d:2’,3’-d’]thieno[3,2-b:3’,2’-b’]dipyrrole

[21], and indeno[1,2-b]thiophene [22]. Recently, our group and Lin have employed

some large conjugated rigid units, i.e., dithieno[2',3':4,5]pyrrolo[3,2-e:2',3'-g][2,1,3]-

benzothiadiazole (DTPBT) [23], dithieno[3',2':3,4;2'',3'':5,6]benzo[1,2-c][1,2,5]oxadi-

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azole (BTBF) [24] and dithieno[3, 2-f:2',3'-h]quinoxaline (DTQ) [25,26], which

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contain a donor-acceptor-donor structure, into the π-bridges and obtained high PCEs.

Actually, dithienopyrrolobenzotriazole (DTBT) is also a donor-acceptor-donor type

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structure similar to the dithienopyrrolobenzothiadiazole (DTPBT). However, to the

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best of our knowledge, it has not been utilized in the sensitizer for DSSCs. In
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comparison to the DTPBT, the electron-withdrawing unit benzotriazole in DTBT

shows less electron deficient property than benzothiadiazole [27]. In addition, a new
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reaction point on 2-position in benzotriazole can be applied to incorporate more alkyl

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chain to suppress the intermolecular aggregation.

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In this work, we designed and synthesized four novel metal-free organic dyes

(DT1-DT4) introducing the DTBT unit as a π-bridge (Fig. 1). The design is based on
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the following considerations: (1) incorporation of large planar DTBT unit can
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effectively delocalize the π-electrons, which can facilitate the intramolecular charge
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transfer (ICT) of the molecules; (2) triphenylamine, dihexyloxyl substituted

triphenylamine and dihexyloxylphenyl substituted triphenylamine are applied as the

electron donor to control the HOMO and LUMO levels and physical properties; (3)

different alkyl chains (hexyl groups and 2-ethylhexyl groups) are introduced into

organic sensitizers to modulate the charge recombination rate and photovoltaic

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performance; (4) the alkyl chains on donors and DTBT can not only improve the

solubility of dyes, but also reduce the intermolecular aggregation and suppress the

charge recombination on the TiO2 films. The photophyscial and electrochemical

properties as well as their application for DSSCs have been discussed.

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Fig. 1. Chemical structure of the dyes DT1-DT4.

Scheme 1.

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Experimental

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1.1.Materials and instruments

All reagents were purchased from J&K, Adamas and Aladdin. THF, toluene and

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1,4-dioxane were distilled over sodium under argon atmosphere. Other solvents were

applied without further purification. The column chromatography separations were

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used on silica gel (300-400 mesh). All reactions were performed under argon
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atmosphere and monitored by thin layer chromatography (TLC).

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1
H and 13C NMR spectra were measured on Bruker 400 and 600 MHz instruments

in CDCl3 and THF-d8. The melting point was conducted on a SGW-X-4B microscopic
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melting point apparatus. HRMS spectra were recorded on an Agilent Technologies

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1290 Infinity mass spectrophotometer. UV-vis absorption spectra of dye solutions and
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dye-adsorbed TiO2 films were measured on Shimadzu UV-2450 spectrophotometer

and UV-3010 spectrophotometer, respectively. The emission spectra of the dyes in

dichloromethane solution were performed on a Fluorolog III photoluminescence.

Cyclic voltammetry (CV) measurements were recorded on a CHI660E

electrochemical workstation using a typical three electrode electrochemical cell in a

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solution of tetrabutylammoniumhexafluorophosphate (TBAPF6) in dry MeCN with a

scan rate of 50 mV s-1. Dye loaded TiO2 film was used as the working electrode, an

Ag/AgCl electrode as the reference electrode and a platinum wire as the counter

electrode. The ferrocene/ferrocenium (Fc/Fc+) redox couple acted as an internal

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potential reference. The electrochemical redox potentials of dyes versus NHE were

calibrated by addition of 0.63 V to the potential versus (Fc/Fc+). The current

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density-voltage (J-V) characteristics of the DSSCs were measured by recording J-V

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curves using a Keithley 2400 source meter under simulated AM 1.5 G (100 mW cm-2)

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illumination with a solar light simulator (Oriel, Model: 91192). The incident
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monochromatic photo-to-current conversion efficiency (IPCE) was performed on a

Spectral Products DK240 monochromator from 300 to 800 nm region. The

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electrochemical impedance spectra (EIS) were measured on Zahner Zennium

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electrochemical workstation under dark station under a forward bias of – 0.75 V with
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a frequency range of 0.1 Hz to 100 kHz.

1.2.Synthesis of dyes
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2.2.1. 4,7-Dibromo-2-hexyl-5,6-dinitro-2H-benzo[d][1,2,3]triazole (2)

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To a solution of 4,7-dibromo-2-hexyl-2H-benzo[d][1,2,3]triazole (1) (3.0 g, 8.3

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mmol) in concentrated sulphuric acid (20 mL), fuming nitric acid (20 mL) was added

slowly over 30 min at 0 oC. Then the mixture was stirred for another 4 h at room

temperature. The reaction mixture was poured into ice water (100 mL), and extracted

with CH2Cl2 three times. The combined organic fractions were washed with water and

dried over MgSO4. The solvent was removed under reduced pressure, and the residue
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was purified by column chromatography on a silica gel column with ethyl

acetate/petroleum ether (v/v = 1/6) as the eluent. 2 was obtained as a yellow solid in

28% yield (1.05 g), mp 93–95 oC. 1H NMR (400 MHz, CDCl3) δ 4.91 (t, J = 7.2 Hz,

2H), 2.29–2.15 (m, 2H), 1.37 (m, 6H), 0.90 (t, J = 6.3 Hz, 3H).13C NMR (100 MHz,

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CDCl3) δ 142.9, 141.9, 107.2, 58.8, 31.0, 29.9, 26.0, 22.3, 13.9. HRMS (ESI, m/z):

[M + Na]+ calcd for C12H1379Br79BrN5NaO4: 471.9226, found: 471.9228; [M + Na]+

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calcd for C12H1379Br81BrN5NaO4: 473.9207, found: 473.9215.

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2.2.2. 2-Hexyl-5,6-dinitro-4,7-di(thiophen-2-yl)-2H-benzo[d][1,2,3]triazole (3)

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To a solution of 2 (800 mg, 1.77 mmol) and tributyl(thiophen-2-yl)stannane (1.53 g,
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4.10 mmol) in THF (25 mL), Pd(PPh3)2Cl2 (125 mg, 0.177 mol) was added as catalyst.

The reaction mixture was stirred for 16 h under argon at 70 oC. Water (50 mL) was
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added to quench the reaction, and the mixture was extracted with CH2Cl2 three times.
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The organic layer was collected, washed with water, dried over MgSO4, filtered and
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concentrated. The crude product was purified by column chromatography on silica gel

column with dichloromethane/petroleum ether (v/v = 2/3) as the eluent. 3 was

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obtained as a yellow solid in 85% yield (687 mg), mp 155–157 oC. 1H NMR (400
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MHz, CDCl3) δ 7.66 (d, J = 5.0 Hz, 2H), 7.54–7.53 (m, 2H), 7.22–7.20 (m, 2H), 4.81
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(t, J = 7.2 Hz, 2H), 2.17–2.10 (m, 2H), 1.40–1.29 (m, 6H), 0.89 (t, J = 6.4 Hz, 3H).13C

NMR (100 MHz, CDCl3) δ 141.7, 139.9, 130.5, 130.5, 129.7, 128.0, 119.6, 58.1, 31.1,

29.9, 26.1, 22.4, 14.0. HRMS (ESI, m/z): [M + H]+ calcd for C20H20N5O4S2: 458.0951,

found: 458.0948.

2.2.3. 5,10,11-Trihexyl-10,11-dihydro-5H-thieno[2',3':4,5]pyrrolo[3,2-g]thieno[3,2-
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b][1,2,3]triazolo[4,5-e]indole (4)

To a solution of 3 (1.37 g, 3 mmol) in o-dichlorobenzene (30 mL), PPh3 (7.87 g, 30

mmol) was added. The reaction mixture was stirred for 18 h under argon at 190 oC.

After cooling to room temperature, the solvent was removed by reduced pressure

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distillation. The residue was purified by column chromatography on a silica gel

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column (ethyl acetate/petroleum ether, v/v = 1/2) to obtain a buff solid. The resulting

buff solid was mixed with 1-bromohexane (2.97 g, 18 mmol), KOH (1.68 g, 30

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mmol), KI (50 mg, 0.30 mmol) and DMSO (60 mL). Then the mixture was stirred

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under argon atmosphere at 85 oC for 16 h. After cooling to room temperature, water
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was added to quench the reaction. The mixture was extracted with ethyl acetate three

times and the combined organic layer was washed with water and brine, then dried
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over MgSO4. After removal of the solvent under reduced pressure, the residue was
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purified by column chromatography on silica gel column with ethyl acetate/petroleum

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ether (v/v = 1/10) as the eluent. 4 was obtained as light yellow solid in 71% yield for

the two steps (1.20 g), mp 104–106 oC. 1H NMR (400 MHz, CDCl3) δ 7.39 (d, J = 5.1
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Hz, 2H), 7.19 (d, J = 5.1 Hz, 2H), 4.81 (t, J = 7.4 Hz, 2H), 4.50–4.41 (m, 4H), 2.22–
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2.15 (m, 2H), 1.78–1.70 (m, 4H), 1.45–1.33 (m, 6H), 1.16–1.07 (m, 12H), 0.89 (t, J =
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6.9 Hz, 3H), 0.76 (t, J = 6.7 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 146.1, 136.0,

131.6, 126.0, 120.10, 112.1, 108.9, 56.2, 50.5, 31.5, 31.4, 30.6, 29.8, 26.5, 26.4, 22.6,

22.5, 14.1, 14.0. HRMS (ESI, m/z): [M + H]+ calcd for C32H44N5S2: 562.3033, found:

562.3041.

2.2.4. 5,10,11-Trihexyl-10,11-dihydro-5H-thieno[2',3':4,5]pyrrolo[3,2-g]thieno[3,2-
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b][1,2,3]triazolo[4,5-e]indole-2-carbaldehyde (5)

To a solution of 4 (332 mg, 0.59 mmol) and DMF (0.23 mL, 2.95 mmol) in

1,2-dichloroethane (20 mL), POCl3 (0.276 mL, 2.95 mmol) was added dropwise for

20 min at 0 oC under argon atmosphere. After addition of POCl3, the reaction mixture

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was stirred at 0 oC for 1h, and then warmed to 50 oC for another 1h. After cooling to

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room temperature, 0.1 M sodium hydroxide aqueous solution (20 mL) was added to

neutralize the solution. The mixture was extracted with CH2Cl2 three times, and the

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combined organic layer was washed with brine and dried over MgSO4. After removal

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of the solvent under reduced pressure, the residue was purified by silica gel column
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chromatography with ethyl acetate/petroleum ether (v/v = 1/6) as the eluent. 5 was

obtained as yellow solid in 93% yield (323 mg), mp 107–109 oC. 1H NMR (400 MHz,
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CDCl3) δ 9.97 (s, 1H), 7.82 (s, 1H), 7.48 (d, J = 4.8 Hz, 1H), 7.20 (d, J = 4.8 Hz, 1H),
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4.81 (t, J = 7.2 Hz, 2H), 4.52–4.46 (m, 4H), 2.23–2.15 (m, 2H), 1.79–1.70 (m, 4H),
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1.47–1.31 (m, 6H), 1.16–1.04 (m, 12H), 0.90 (t, J = 6.6 Hz, 3H), 0.78–0.74 (m, 6H).

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C NMR (100 MHz, CDCl3) δ 183.0, 147.3, 144.9, 142.7, 136.1, 135.9, 135.1, 130.2,
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128.5, 127.9, 120.1, 112.0, 112.1, 111.6, 108.4, 56.3, 50.7, 50.6, 31.4, 31.3, 31.3, 30.5,
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29.9, 29.9, 26.5, 26.4, 26.4, 22.6, 22.5, 22.5, 14.1, 13.9. HRMS (ESI, m/z): [M + H]+
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calcd for C33H44N5OS2: 590.2982, found: 590.2976.

2.2.5. 8-Bromo-5,10,11-trihexyl-10,11-dihydro-5H-thieno[2',3':4,5]pyrrolo[3,2-

g]thieno[3,2-b][1,2,3]triazolo[4,5-e]indole-2-carbaldehyde (6)

To a solution of 5 (158 mg, 0.27 mmol) in THF (15 mL), NBS (72 mg, 0.41 mmol)

was added in one portion. The mixture was stirred at 0 oC for 5 h. After completion of
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the reaction, the mixture was poured into water and extracted with CH2Cl2 three times.

The combined organic fraction was washed with water and dried over MgSO4. After

evaporation of the solvent under reduced pressure, the residue was purified by column

chromatography on a silica gel column with ethyl acetate/petroleum ether (v/v = 1/6)

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as the eluent. 6 was obtained as a yellow solid in 96% yield (180 mg), mp 127–129 oC.

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H NMR (400 MHz, CDCl3) δ 9.98 (s, 1H), 7.82 (s, 1H), 7.24 (s, 1H), 4.79 (t, J = 7.3

Hz, 2H), 4.50–4.40 (m, 4H), 2.21–2.14 (m, 2H), 1.80–1.68 (m, 4H), 1.46–1.31 (m,

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6H), 1.17–1.06 (m, 12H), 0.90 (t, J = 6.8 Hz, 3H), 0.78–0.75 (m, 6H). 13C NMR (100

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MHz, CDCl3) δ 183.0, 145.0, 144.8, 142.9, 136.0, 135.7, 134.8, 129.2, 128.3, 120.1,
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120.0, 115.4, 114.5, 111.2, 108.5, 56.3, 50.7, 50.6, 31.4, 31.3, 30.4, 30.0, 26.4, 26.4,

26.4, 22.6, 22.5, 14.1, 13.9. HRMS (ESI, m/z): [M + H]+ calcd for C33H4379BrN5OS2:
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668.2087, found: 668.2083; [M + H]+ calcd for C33H4381BrN5OS2: 670.2070, found:

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670.2071.
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2.2.6. 8-(4-(Diphenylamino)phenyl)-5,10,11-trihexyl-10,11-dihydro-5H-thieno[2',3':4,

5]pyrrolo[3,2-g]thieno[3,2-b][1,2,3]triazolo[4,5-e]indole-2-carbaldehyde (8a)
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To a solution of 6 (170 mg, 0.25 mmol), (4-(diphenylamino)phenyl)boronic acid

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(7a) (110 mg, 0.38 mmol), and 2 M aqueous K2CO3 solution (0.38 mL) in THF,
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Pd(PPh3)4 (29 mg, 0.025 mmol) was added as catalyst. The reaction mixture was

stirred under argon atmosphere at 70 oC for 16 h. After cooling to room temperature,

the reaction was quenched by water and the mixture was extracted with CH2Cl2. The

organic layer was dried over MgSO4 and evaporated by reduced pressure. The residue

was purified by column chromatography on silica gel column with ethyl

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acetate/petroleum ether (v/v = 1/6) as the eluent. 8a was obtained as a red solid in 79%

yield (164 mg), mp 120–122 oC. 1H NMR (400 MHz, CDCl3) δ 9.95 (s, 1H), 7.79 (s,

1H), 7.62–7.60 (m, 2H), 7.32–7.28 (m, 5H), 7.18–7.05 (m, 8H), 4.80 (t, J = 7.3 Hz,

2H), 4.47–4.43 (m, 4H), 2.23–2.15 (m, 2H), 1.83–1.77 (m, 4H), 1.46–1.32 (m, 6H),

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1.18–1.11 (m, 12H), 0.92–0.89 (m, 3H), 0.80–0.75 (m, 6H). C NMR (100 MHz,

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CDCl3) δ 182.9, 147.7, 147.7, 147.5, 146.8, 144.9, 142.6, 136.0, 135.0, 129.5, 129.4,

129.2, 128.5, 126.5, 124.8, 123.7, 123.4, 120.0, 118.7, 111.7, 108.1, 106.9, 56.2, 50.6,

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50.5, 31.4, 31.3, 30.4, 30.0, 29.9, 26.4, 26.4, 22.6, 22.5, 14.1, 13.9. HRMS (ESI, m/z):

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[M + H]+ calcd for C51H57N6OS2: 833.4030, found: 833.4034.
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2.2.7.8-(4-(Bis(4-(hexyloxy)phenyl)amino)phenyl)-5,10,11-trihexyl-10,11-dihydro-5

H-thieno[2',3':4,5]pyrrolo[3,2-g]thieno[3,2-b][1,2,3]triazolo[4,5-e]indole-2-carbaldeh
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yde (8b)
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The synthesis method of 8b was similar to that of 8a, except

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4-(hexyloxy)-N-(4-(hexyloxy)phenyl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2

-yl)phenyl)aniline (7b) instead of 7a. 8b was obtained as a red solid in 68% yield (176
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mg), mp 44–46 oC. 1H NMR (400 MHz, CDCl3) δ 9.96 (s, 1H), 7.80 (s, 1H), 7.53 (d,
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J = 8.1 Hz, 2H), 7.26 (s, 1H), 7.09 (d, J = 8.1 Hz, 4H), 6.96 (d, J = 8.1 Hz, 2H), 6.85
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(d, J = 8.1 Hz, 4H), 4.80 (t, J = 7.1 Hz, 2H), 4.50–4.44 (m, 4H), 3.95 (t, J = 6.4 Hz,

4H), 2.22–2.15 (m, 2H), 1.82–1.75 (m, 8H), 1.47–1.45 (m, 6H), 1.35 (m, 12H), 1.17–

1.10 (m, 12H), 0.93–0.90 (m, 9H), 0.79–0.75 (m, 6H). 13C NMR (100 MHz, CDCl3) δ

182.8, 155.9, 148.7, 147.8, 147.3, 144.8, 142.4, 140.4, 136.0, 135.0, 129.2, 128.5,

127.1, 126.9, 126.3, 120.3, 119.9, 118.3, 115.5, 111.8, 107.9, 106.3, 68.4, 56.2, 50.5,
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50.4, 31.7, 31.4, 31.3, 30.4, 29.9, 29.9, 29.4, 26.4, 26.4, 25.9, 22.7, 22.6, 22.5, 14.1,

14.1, 13.9. HRMS (ESI, m/z): [M + H]+ calcd for C63H81N6O3S2: 1033.5806, found:

1033.5814.

2.2.8. 8-(4-(Bis(4'-(hexyloxy)-[1,1'-biphenyl]-4-yl)amino)phenyl)-5,10,11-trihexyl-10,

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11-dihydro-5H-thieno[2',3':4,5]pyrrolo[3,2-g]thieno[3,2-b][1,2,3]triazolo[4,5-e]indole

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-2-carbaldehyde (8c)

The synthesis of 8c was similar to that of 8a, except 4'-(hexyloxy)-N-(4'-

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(hexyloxy)-[1,1'-biphenyl]-4-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)p

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henyl)-[1,1'-biphenyl]-4-amine (7c) instead of 7a. 8c was obtained as a red solid in 63%
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yield (186 mg), mp 129–131 oC. 1H NMR (400 MHz, CDCl3) δ 9.96 (s, 1H), 7.81 (s,

1H), 7.65–7.63 (m, 2H), 7.53–7.48 (m, 8H), 7.34 (s, 1H), 7.23–7.19 (m, 6H), 6.98–
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6.95 (m, 4H), 4.81 (t, J = 7.1 Hz, 2H), 4.51–4.46 (m, 4H), 4.00 (t, J = 6.4 Hz, 4H),
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2.23–2.15 (m, 2H), 1.84–1.72 (m, 8H), 1.48–1.43 (m, 6H), 1.36 (m 12H), 1.17–1.11
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(m, 12H), 0.92–0.88 (m, 9H), 0.79–0.76 (m, 6H). C NMR (100 MHz, CDCl3) δ

182.9, 158.7, 147.7, 147.5, 146.8, 146.1, 144.9, 142.6, 136.0, 135.9, 135.0, 133.0,
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129.5, 129.4, 128.6, 127.8, 127.6, 126.6, 125.0, 123.8, 119.9, 118.8, 115.0, 111.8,
C

108.2, 107.0, 68.2, 56.3, 50.6, 50.5, 31.7, 31.4, 31.4, 30.5, 30.0, 29.4, 26.5, 26.4, 25.9,
AC

22.7, 22.61, 22.5, 14.2, 14.1, 14.0. HRMS (ESI, m/z): [M + H]+ calcd for

C75H89N6O3S2: 1185.6432, found: 1185.6479.

2.2.9. 10,11-Bis(2-ethylhexyl)-5-hexyl-10,11-dihydro-5H-thieno[2',3':4,5]pyrrolo[3,2-

g]thieno[3,2-b][1,2,3]triazolo[4,5-e]indole (9)

The synthesis method of 9 was similar to that of 4, except 2-ethylhexyl bromide

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instead of 1-bromohexane. 9 was obtained as a viscous liquid in 67% yield for two

steps. 1H NMR (400 MHz, CDCl3) δ 7.37 (d, J = 4.5 Hz, 2H), 7.16 (d, J = 4.5 Hz, 2H),

4.81 (t, J = 7.3 Hz, 2H), 4.54–4.44 (m, 4H), 2.25–2.18 (m, 2H), 1.92–1.90 (m, 2H),

13
1.50–1.33 (m, 6H), 0.99–0.78 (m, 19H), 0.63–0.58 (m, 12H). C NMR (100 MHz,

PT
CDCl3) δ 145.5, 136.1, 131.9, 125.5, 119.8, 112.4, 108.5, 56.2, 54.2, 39.4, 31.5, 30.5,

29.8, 27.9, 26.6, 23.3, 22.8, 22.6, 14.1, 13.8, 10.2. HRMS (ESI, m/z): [M + H]+ calcd

RI
for C36H52N5S2: 618.3659, found: 618.3658.

SC
2.2.10. 10,11-Bis(2-ethylhexyl)-5-hexyl-10,11-dihydro-5H-thieno[2',3':4,5]pyrrolo[3,

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2-g]thieno[3,2-b][1,2,3]triazolo[4,5-e]indole-2-carbaldehyde (10)
AN
Compound 10 was synthesized from 9 according to the same procedure as that of 5,

as a yellow viscous liquid in 90% yield. 1H NMR (400 MHz, CDCl3) δ 9.97 (s, 1H),
M

7.79 (s, 1H), 7.47–7.45 (m, 1H), 7.17–7.16(m, 1H), 4.80 (t, J = 7.2 Hz, 2H), 4.53–
D

4.47 (m, 4H), 2.24–2.17 (m, 2H), 1.93–1.87 (m, 2H), 1.47–1.32 (m, 6H), 0.99–0.79
TE

13
(m, 19H), 0.62–0.60 (m, 12H). C NMR (100 MHz, CDCl3) δ 183.0, 146.8, 144.4,

142.5, 136.2, 136.0, 135.5, 130.6, 128.2, 127.5, 120.2, 119.9, 112.4, 111.2, 108.0, 56.3,
EP

54.4, 54.3, 39.5, 39.5, 31.4, 30.4, 29.8, 29.8, 27.9, 27.9, 26.5, 23.4, 23.3, 22.8, 22.8,
C

22.6, 14.1, 13.8, 13.8, 10.2. HRMS (ESI, m/z): [M + H]+ calcd for C37H52N5OS2:
AC

646.3608, found: 646.3606.

2.2.11. 8-Bromo-10,11-bis(2-ethylhexyl)-5-hexyl-10,11-dihydro-5H-thieno[2',3':4,5]-

pyrrolo[3,2-g]thieno[3,2-b][1,2,3]triazolo[4,5-e]indole-2-carbaldehyde (11)

Compound 11 was obtained from 10 using the same synthesis procedure as that of 6,

as a yellow viscous liquid in 95% yield. 1H NMR (400 MHz, CDCl3) δ 9.97 (s, 1H),
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7.79 (s, 1H), 7.21 (s, 1H), 4.78 (t, J = 7.2 Hz, 2H), 4.50–4.41 (m, 4H), 2.22–2.15 (m,

2H), 1.90–1.84 (m, 2H), 1.46–1.32 (m, 6H), 0.98–0.79 (m, 19H), 0.61 (m, 12H). 13C

NMR (100 MHz, CDCl3) δ 183.0, 144.5, 144.3, 142.7, 136.0, 135.8, 135.2, 129.6,

128.1, 120.2, 119.9, 115.6, 114.2, 110.9, 108.2, 56.3, 54.4, 54.4, 39.5, 31.4, 30.4, 29.8,

PT
29.7, 27.9, 27.8, 27.8, 26.5, 23.3, 22.8, 22.8, 22.6, 14.1, 13.8, 10.2, 10.2. HRMS (ESI,

m/z): [M + Na]+ calcd for C37H5079BrN5NaOS2: 746.2532, found: 746.2534; [M +

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Na]+ calcd for C37H5081BrN5NaOS2: 748.2517, found: 748.2516.

SC
2.2.12.8-(4-(Diphenylamino)phenyl)-10,11-bis(2-ethylhexyl)-5-hexyl-10,11-dihydro-

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5H-thieno[2',3':4,5]pyrrolo[3,2-g]thieno[3,2-b][1,2,3]triazolo[4,5-e]indole-2-carbalde
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hyde (12)

The synthesis procedure of 12 was similar to that of 8a. 12 was obtained as a red
M

solid in 76% yield, mp 67–69 oC. 1H NMR (400 MHz, CDCl3) δ 9.96 (s, 1H), 7.79 (s,
D

1H), 7.62–7.59 (m, 2H), 7.31–7.27 (m, 5H), 7.16–7.11 (m, 6H), 7.08–7.04 (m, 2H),
TE

4.81 (t, J = 7.4 Hz, 2H), 4.53–4.48 (m, 4H), 2.24–2.17 (m, 2H), 1.95–1.88 (m, 2H),

1.49–1.32 (m, 6H), 1.04–0.97 (m, 6H), 0.91–0.84 (m, 13H), 0.65–0.60 (m, 12H). 13C
EP

NMR (100 MHz, CDCl3) δ 183.0, 147.7, 147.6, 147.2, 146.4, 144.4, 142.3, 136.1,
C

136.1, 135.5, 129.9, 129.5, 129.4, 128.3, 126.5, 124.8, 123.7, 123.4, 120.2, 118.5,
AC

111.4, 107.9, 107.2, 56.3, 54.4, 54.3, 39.5, 39.5, 31.4, 30.4, 29.8, 29.8, 27.9, 26.5,

23.3, 23.3, 22.8, 22.6, 14.1, 13.8, 10.2. HRMS (ESI, m/z): [M + Na]+ calcd for

C55H64N6NaOS2: 911.4475, found: 911.4479.

2.2.13. (E)-2-Cyano-3-(8-(4-(diphenylamino)phenyl)-5,10,11-trihexyl-10,11-dihydro-

5H-thieno[2',3':4,5]pyrrolo[3,2-g]thieno[3,2-b][1,2,3]triazolo[4,5-e]indol-2-yl)acrylic
 ACCEPTED MANUSCRIPT

acid (DT1)

A solution of 8a (120 mg, 0.144 mmol), ammonium acetate (33.3 mg, 0.432 mmol),

tert-butyl 2-cyanoacetate (61.0 mg, 0.432 mmol) and acetic acid (2 mL) in toluene (20

mL) was stirred under argon at 130 oC for 3 h. after cooling to room temperature, the

PT
reaction mixture was quenched by adding water and extracted with CH2Cl2. The

RI
combined organic fraction was dried over MgSO4 and the solvent was evaporated by

reduced pressure. The residue was purified by silica gel column chromatography

SC
(ethyl/ dichloromethane/ petroleum ether, v/v/v = 1/1/6) to give a purple solid. The

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resulting solid was dissolved in trifluoracetic acid (15 mL), and stirred at room
AN
temperature for 3 h. After completion of the reaction, the mixture was poured into

water (80 mL), and the resulting crude product was collected by filtration and washed
M

with water (300 mL) to give DT1 as a purple solid, mp 212–214 oC. The yield for the
D

two steps was 71% yield (92.0 mg). 1H NMR (400 MHz, THF-d8) δ 8.42 (s, 1H), 8.12
TE

(s, 1H), 7.67–7.65 (m, 2H), 7.60 (s, 1H), 7.29–7.25 (m, 4H), 7.13–7.09 (m, 6H), 7.05–

7.01 (m, 2H), 4.79 (t, J = 7.0 Hz, 2H), 4.61 (m, 4H), 2.20–2.13 (m, 2H), 1.85–1.78 (m,
EP

4H), 1.45–1.32 (m, 6H), 1.16–1.12 (m, 12H), 0.92–0.89 (m, 3H), 0.77–0.73 (m, 6H).
C

13
C NMR (100 MHz, THF-d8) δ 164.8, 149.0, 148.5, 147.5, 147.3, 146.4, 136.8, 136.7,
AC

136.6, 135.6, 130.5, 130.1, 130.1, 129.7, 127.1, 125.4, 124.5, 124.0, 121.7, 119.3,

117.4, 112.8, 108.9, 108.3, 97.0, 56.6, 51.3, 51.1, 32.3, 32.2, 32.1, 31.2, 30.7, 30.6,

30.6, 27.3, 27.1, 27.1, 23.4, 23.3, 23.3, 14.4, 14.2. HRMS (ESI, m/z): [M + H]+ calcd

for C54H58N7O2S2: 900.4088, found: 900.4085.

2.2.14. (E)-3-(8-(4-(Bis(4-(hexyloxy)phenyl)amino)phenyl)-5,10,11-trihexyl-10,11-
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dihydro-5H-thieno[2',3':4,5]pyrrolo[3,2-g]thieno[3,2-b][1,2,3]triazolo[4,5-e]indol-2-y

l)-2-cyanoacrylic acid (DT2)

Compound DT2 synthesized from 8b uses the same procedure to that of DT1. DT2

was obtained as a purple solid in 67% yield, mp 185–187 oC. 1H NMR (400 MHz,

PT
THF-d8) δ 8.42 (s, 1H), 8.13 (s, 1H), 7.56 (d, J = 8.2 Hz, 2H), 7.52 (s, 1H), 7.06 (d, J

RI
= 8.4 Hz, 4H), 6.93 (d, J = 8.2 Hz, 2H), 6.86 (d, J = 8.4 Hz, 4H), 4.79 (t, J = 7.1 Hz,

2H), 4.63–4.58 (m, 4H), 3.95 (t, J = 6.3 Hz, 4H), 2.20–2.13 (m, 2H), 1.82–1.75 (m,

SC
8H), 1.52–1.37 (m, 18H), 1.19–1.14 (m, 12H), 0.94–0.89 (m, 9H), 0.78–0.72 (m, 6H).

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13
C NMR (100 MHz, THF-d8) δ 164.7, 157.0, 149.7, 149.2, 148.0, 147.6, 146.4, 141.3,
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136.8, 136.6, 136.5, 135.7, 129.8, 128.2, 127.6, 127.5, 126.9, 121.8, 121.1, 118.8,

117.4, 116.0, 113.0, 108.7, 107.6, 96.7, 68.8, 56.6, 51.3, 51.1, 32.6, 32.3, 32.2, 32.1,
M

31.2, 30.7, 30.6, 30.5, 30.3, 27.3, 27.1, 26.7, 23.5, 23.4, 23.3, 23.2, 14.4, 14.2. HRMS
D

(ESI, m/z): [M + Na]+ calcd for C66H81N7NaO4S2: 1122.5684, found: 1122.5692.

TE

2.2.15. (E)-3-(8-(4-(Bis(4'-(hexyloxy)-[1,1'-biphenyl]-4-yl)amino)phenyl)-5,10,11-

trihexyl-10,11-dihydro-5H-thieno[2',3':4,5]pyrrolo[3,2-g]thieno[3,2-b][1,2,3]triazolo-
EP

[4,5-e]indol-2-yl)-2-cyanoacrylic acid (DT3)

C

The synthesis procedure of DT3 was similar to that of DT1. DT3 was obtained as a
AC

red solid in 70% yield, mp 231–233 oC. 1H NMR (400 MHz, THF-d8) δ 8.42 (s, 1H),

8.12 (s, 1H), 7.70–7.67 (m, 2H), 7.62 (s, 1H), 7.54–7.52 (m, 8H), 7.20–7.16 (m, 6H),

6.95–6.93 (m, 4H), 4.79 (t, J = 7.0 Hz, 2H), 4.62–4.59 (m, 4H), 3.97 (t, J = 6.3 Hz,

4H), 2.20–2.13 (m, 2H), 1.86–1.76 (m, 8H), 1.51–1.36 (m, 18H), 1.16–1.14 (m, 12H),

0.92–0.89 (m, 9H), 0.78–0.73 (m, 6H). 13C NMR (100 MHz, THF-d8) δ 164.6, 159.7,
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149.1, 148.4, 147.6, 147.4, 147.0, 146.4, 136.8, 136.8, 136.6, 136.6, 135.7, 133.6,

130.5, 130.1, 129.8, 128.2, 128.1, 127.1, 125.7, 124.5, 121.7, 119.3, 117.3, 115.5,

112.9, 108.9, 108.3, 96.7, 68.6, 56.7, 51.3, 51.1, 32.6, 32.3, 32.2, 32.1, 31.2, 30.7,

30.6, 30.3, 27.3, 27.1, 27.1, 26.7, 23.5, 23.4, 23.3, 23.3, 14.4, 14.4, 14.2. HRMS (ESI,

PT
m/z): [M + Na]+ calcd for C78H89N7NaO4S2: 1274.6310, found: 1274.6329.

RI
2.2.16. (E)-2-Cyano-3-(8-(4-(diphenylamino)phenyl)-10,11-bis(2-ethylhexyl)-5-

hexyl-10,11-dihydro-5H-thieno[2',3':4,5]pyrrolo[3,2-g]thieno[3,2-b][1,2,3]triazolo[4,

SC
5-e]indol-2-yl)acrylic acid (DT4)

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The synthesis procedure of DT4 was similar to that of DT1. DT4 was obtained as a
AN
red solid in 65% yield, mp 202–204 oC. 1H NMR (400 MHz, THF-d8) δ 8.42 (s, 1H),

8.15 (s, 1H), 7.67–7.65 (m, 2H), 7.58 (s, 1H), 7.29–7.25 (m, 4H), 7.13–7.09 (m, 6H),
M

7.05–7.01 (m, 2H), 4.79 (t, J = 7.1 Hz, 2H), 4.66–4.61 (m, 4H), 2.21–2.14 (m, 2H),
D

2.04–2.00 (m, 2H), 1.48–1.33 (m, 8H), 1.07–0.89 (m, 17H), 0.68–0.58 (m, 12H). 13C
TE

NMR (150 MHz, THF-d8) δ 164.7, 148.6, 148.5, 147.5, 147.1, 146.0, 136.8, 136.6,

136.5, 136.1, 130.6, 130.5, 130.2, 130.1, 129.4, 127.1, 125.4, 124.5, 124.0, 121.7,
EP

119.2, 117.4, 112.6, 108.7, 108.6, 97.2, 56.7, 55.0, 54.9, 40.4, 32.3, 31.1, 30.6, 30.5,
C

30.4, 28.5, 28.5, 28.5, 28.5, 27.3, 24.0, 23.9, 23.6, 23.4, 14.3, 14.0, 10.4, 10.4, 10.3.
AC

HRMS (ESI, m/z): [M + Na]+ calcd for C58H65N7NaO2S2: 978.4533, found: 978.4534.

1.3.Computational details

The ground state geometries were calculated employing B3LYP function and

6-31G* basis set. The vertical excitation energies were calculated by TD-DFT at

MPW1K/6-31 G** levels [14]. CH2Cl2 was selected as the solvent. The solvent effect
 ACCEPTED MANUSCRIPT

was simulated by the conductor-like polarizable continuum model (C-PCM) [28]. All

the calculations were conducted on the Gaussian 09 program package.

1.4.Fabrication of dye-sensitized solar cells

The TiO2 films (~12 µm in thickness) with a scattering layer (~4 µm) were prepared

PT
according to previous procedure [29]. The active area of the TiO2 film was 0.4 × 0.4

cm-2. The TiO2 photoanodes were dipped into a solution of CH2Cl2 containing 0.3

RI
mM dye for 16 h in the dark. For the co-adsorbed solar cell, chenodeoxycholic acid

SC
(CDCA) was added into the sensitizer solutions. After adsorption of the sensitizers,

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the films were rinsed with CH2Cl2 and dried. The dye-sensitized TiO2/FTO
AN
photoanode together with the Pt/FTO counter electrode were assembled into

sandwiched type solar cells. The electrolyte (0.6 M 1-metyl-3-propylimidazolium

M

iodide (PMII), 0.1 M guanidinium thiocyanate, 0.07 M I2, 0.05 M LiI, and 0.5 M
D

tert-butylpyridine in acetonitrile/ valeronitrile (85:15)) was injected into the seam

TE

between the two electrodes.

2. Results and discussion

EP

2.1.Synthesis of the materials

C

The synthesis route of DT1-DT4 is outlined in Scheme 1. 4,7-Dibromo-2-

AC

hexyl-2H-benzo[d][1,2,3]triazole (1) [30], 4-(hexyloxy)-N-(4-(hexyloxy)phenyl)-

N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)aniline (7b) [26] and

4'-(hexyloxy)-N-(4'-(hexyloxy)-[1,1'-biphenyl]-4-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-

dioxaborolan-2-yl)- phenyl)[1,1'-biphenyl]-4-amine (7c) [31] were synthesized

according to the references. The nitration of 1 using concentrated sulfuric acid and
 ACCEPTED MANUSCRIPT

nitrosonitric acid afforded the nitrocompound 2. 2 was then reacted with

2-tributylstannyl thiophene by Stille coupling reaction to yield compound 3. A double

intramolecular Cadogan reductive cyclization of 3 in the presence of

triphenylphosphine, and then an N-alkylation reaction obtained the important

PT
intermediate 4. The aldehyde 5 was prepared from 4 through a Vilsmeier-Haack

RI
reaction and then converted to brominated monomer 6 by bromination with

N-bromosuccinimide (NBS). 8a-c were obtained from Pd(PPh3)4 catalyzed Suzuki

SC
coupling reactions of 6 with borate 7a-c. The Knoevenagel condensation reactions of

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8a-c with tert-butyl 2-cyanoacetate afforded their cyanoacetates. The cyanoacetates
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were hydrolyzed with trifluoroacetic acid to provide the target products DT1-DT3.

The synthesis of DT4 with two 2-ethylhexyl chains in the π-bridge was similar to that
M

of DT1 except 2-ethylhexyl bromide instead of 1-bromohexane in the N-alkylation

D

reaction.
TE

2.2.Photophysical properties

The UV-vis absorption and emission spectra of DT1-DT4 in CH2Cl2 solutions (2 ×

EP

10-5 M) are depicted in Fig. 2, and the corresponding data are summarized in Table 1.
C

The UV-vis absorption spectra of DT1-DT4 in the solution exhibit an intense peak
AC

around 550 nm, which can be ascribed to ICT from the donor to the cyanoacrylic acid

acceptor. In comparison with DT1, the maximum absorption wavelengths (λmax) of

DT2 and DT3 show a red-shift of 7 and 3 nm, respectively. This phenomenon can be

attributed to the changed donor increasing the electron-donating ability and extended

the π-conjugation system, which enhances the extent of electron delocalization over
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the whole molecule. The λmax of DT1 and DT4 are the same, which is because the two

dyes contain the same conjugation skeleton. It is worth noting that the four dyes have

high molar extinction coefficients (ε: 59430 to 70802 M-1 cm-1), which indicates that

DT1-DT4 have excellent light harvesting ability. Apparently, the high values of ε of

PT
the four dyes may be due to the incorporation of the large planar structure of DTBT

RI
[23,32,33]. We have also measured the absorption spectra of the four dyes in different

solvents (DCM, CHCl3, THF and DMF) (2 × 10-5 M). As shown in Fig. S1-S4, the

SC
maximum absorption wavelengths (λmax) of DT1-DT4 are significantly affected by the

U
different polarity solvents. The maximum absorption wavelengths of the four dyes in
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different solvents decrease in order of CHCl3 > DCM > THF > DMF. The blue shifts

observed for the dyes in THF and DMF with respect to that in DCM may be ascribed
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to that the higher quantities of polar solvent decrease the electron-withdrawing ability
D

of the carboxylic acid due to its partial deprotonation in the excited state [34,35]. On
TE

the other hand, the bathochromic shift observed for the donor-acceptor molecules in

chlorosolvents has been attributed to the fast rearrangement of the polarizable

EP

electrons during electronic excitation, which is well documented in the literature [36].
C

The normalized absorption spectra of DT1-DT4 on TiO2 films are shown in Fig. 3.
AC

After adsorption of the four dyes on the TiO2 films, a broadening spectra of DT1-DT4

can be found in comparison with the spectra in the solutions, which is beneficial to

improve light harvesting and short-circuit current (Jsc). The maximum absorption

peaks for DT1-DT4 in the TiO2 surfaces are at 477, 471, 466 and 491 nm,

respectively, which are hypsochromic shift of 71, 84, 85 and 57 nm respect to those in
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CH2Cl2 solutions. Such a significant blueshift of the λmax can be attributed to the

deprotonation and/or H-aggregation of the dye molecules upon adsorption [37,38].

DT4 displays smaller blue-shift compared to the other three dyes, which may

indicates that the branched alkyl chains can better reduce the intermolecular π-π

PT
interactions of the molecules than the liner alkyl chains [39,40].

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Fig. 2. Absorption spectra (a) and emission spectra (b) of DT1-DT4 in CH2Cl2

solutions.

SC
Fig. 3. Absorption spectra of DT1-DT4 on TiO2 films.

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Table 1. Photophysical and electrochemical parameters of DT1-DT4.
AN
2.3.Electrochemical properties

Cyclic voltammetry was carried out to investigate the redox properties of the four
M

sensitizers. The cyclic voltammograms are exhibited in Fig. 4, and the associated
D

electrochemical data are listed in Table 1. The estimated ground state oxidation versus
TE

normal hydrogen electrode (vs. NHE) is corresponding to highest occupied molecular

orbital (HOMO) energy level of dye molecule. The HOMO levels of DT1-DT4 are
EP

0.89, 0.78, 0.88 and 0.88 V, respectively. Apparently, the HOMO levels are more
C

positive than I-/I3- redox couples (0.4 V vs. NHE) [41], indicating the driving force for
AC

dye regeneration are sufficient. The energy gaps E0-0 of DT1-DT4 determined from

the intersection point of the normalized absorption and emission spectra are 2.04, 2.06,

2.05 and 2.04 eV, respectively. The LUMO levels calculated from the equation,

LUMO = HOMO – E0-0, are –1.15, –1.28, –1.17 and –1.16 V, respectively. The

LUMO values of the four dyes are all more negative than the conduction edge (–0.5 V
 ACCEPTED MANUSCRIPT

vs. NHE) [42] of TiO2, which implies that electron injection from the excited dye to

the TiO2 film is energetically permitted. The HOMO energy level value of DT2 is

more negative than the other three dyes, indicating an electron-richer feature of

dihexyloxy-substituted triphenylamine than triphenylamine and dihexyloxybenzene-

PT
substituted triphenyl-amine. From the view of the photophysical and electrochemical

RI
data, we thereby conclude that the different alkyl chains on the DTBT unit of the DT1

and DT4 has a less pronounced effect on the physical and electrochemical properties.

SC
Fig. 4. Cyclic voltammograms of DT1-DT4.

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2.4.Molecular orbital calculation
AN
Density functional theory (DFT) calculations at the B3LYP/6-31G* level were

carried out to further understand the geometrical configurations and electron

M

distributions of the four sensitizers. It can be clearly found from Table 2 that for all
D

sensitizers, the HOMO is mainly distributed on the electron donor and extended to the
TE

DTBT unit, while the LUMO is predominantly delocalized over the cyanoacetic acid

segment and partly on the nearby π-bridge. These kinds of electron distributions allow
EP

significant charge transfer from the dyes to the TiO2 films upon photoexcitation. In
C

the view of the optimized structure of the dyes, DTBT unit is a large planar structure,
AC

which shows well coplanar ability. Time dependent density theory calculations

(TD-DFT) were also performed to better understand the excitation energies and

transition assignments of absorption bands of DT1-DT4 (Table 3). From the view of

the data, the maximum absorptions of DT1-DT4 mainly come from the transition

from HOMO LUMO, and small part from HOMO–1 LUMO. Taking DT1 as an
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example, two distinct bands in the absorption spectra are generated form several kinds

of electron excitations. The low energy band located at wavelength longer than 500

nm is mainly ascribed to HOMO LUMO (83.9%) and partially from HOMO–1

LUMO (11.4%) transitions. While the other band in the 300-400 nm region chiefly

PT
comes from HOMO LUMO+1 (83.9%).

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Table 2. Optimized structures and electron distributions in HOMO and LUMO levels

of DT1-DT4.

SC
Table 3. Calculated TD-DFT Wavelengths, Excitation energies (eV), and

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Composition in terms of Molecular Orbital Contributions of the dyes DT1-DT4 with
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Oscillator Strengths (f) larger than 0.5.

2.5.Photovoltaic performance of DSSCs

M

Fig. 5 exhibits the incident photon-to-current conversion efficiency (IPCE) curves

D

of DSSCs based on DT1-DT4. It is quite clear that the devices based on the four dyes
TE

show broad spectral response, covering the entire visible region and part of

near-infrared (NIR) region. The broad spectral responses are agreed with the
EP

absorption spectra of dyes on TiO2 films (Fig. 3). As shown in Fig. 5, DT4 shows a
C

better IPCE performance than the other three dyes, which obtains IPCE value exceed
AC

60% from 400 to 610 nm region and with a maximum value of 67% at 570 nm. This

result is well in consistent with the Jsc value obtained in J-V measurements.

Meanwhile, DT1, DT2 and DT3 get maximum IPCE values of 49% at 570 nm, 53%

at 570 nm and 57% at 560 nm, respectively. Impressively, DT2 and DT3 with a more

electron-richer donor show a much broader IPCE response than those of the other two
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sensitizers. The IPCE as a function of wavelength is directly related to the

light-harvesting efficiency, charge injection efficiency and charge collection

efficiency [43]. For a dye-loaded film with thickness over 10 µm, light-harvesting

efficiency can be considered to be 100% [40]. In addition, the HOMO levels are

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similar to each other for dyes DT1 and DT4. Therefore, the better IPCE performance

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of DT4 than DT1 should be ascribed to the introduced branched 2-ethylhexyl groups,

which better interrupts the intermolecular interactions and thus improves the electron

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injection efficiency. The IPCE performance of the DSSCs with DT3 is higher than

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that with DT1 due to its relatively higher molar extinction coefficient. In addition,
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two hexyloxyphenyl substituted on the triphenylamine can help to suppress the dye

aggregation on TiO2 film, and then improve the electron injection efficiency of DT3
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compared to DT1. The IPCE performance of DT2 is also better than that of DT1 due
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to its broader photocurrent action spectrum and higher LUMO energy level.
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Fig. 5. IPCE spectra of the DSSCs based on DT1-DT4.

Table 4. Photovoltaic performance parameters of the DSSCs based on DT1-4.

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The power conversion efficiencies of the DSSCs sensitized by DT1-DT4 were

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obtained by measuring the J-V characteristics at 100 mW cm-2 simulated AM 1.5G

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solar light (Fig. 6). The detailed photovoltaic parameters of Jsc, open-circuit voltage

(Voc), fill factor (FF) and power conversion efficiency (η) are summarized in Table 4.

Obviously, the DSSC sensitized by DT4 exhibits the best η of 8.05%, with a Jsc of

16.35 mA cm-2, a Voc of 723 mV, and FF of 0.68. The other three cells sensitized by

DT1-3 obtain efficiencies of 5.01%, 5.27% and 5.86%, respectively. For DT1-DT3,
 ACCEPTED MANUSCRIPT

the efficiency of the solar cell can be improved when changed the donor from

triphenylamine to dihexyloxyl substituted triphenylamine and dihexyloxylphenyl

substituted triphenylamine. The variation of Jsc values are agreed with the results

obtained in IPCE measurement. The best DSSC performance of DT4 is due to its

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highest Jsc and Voc. The higher Jsc of DT4 can be attributed to that the incorporated

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branched 2-ethylhexyl groups better restrict the intermolecular interactions. The

highest value of Voc of DT4 may result from the better charge recombination

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suppression than those of the other three dyes (vide infra). DT2 with two hexyloxy

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substitutes in the donor even shows lower Voc value than DT1. This phenomenon may
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be ascribed to the upshift of HOMO energy level of DT2, resulting in a smaller

difference between the HOMO level of the sensitizer and the redox potential of I-/I3-
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couple, leading to a slower dye regeneration rate [44]. Therefore, a slower dye
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regeneration rate would lead to potential back reaction at the TiO2/dye/electrolyte

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interface. From the view of the Voc data of DT1-DT4, in comparison with DT1, the

Voc values of DT2 and DT3 decreased, however, the Voc value of DT4 improved. This
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phenomenon may suggest that the introduction of alkyl chains in the donor part
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cannot effectively restrain the charge recombination and then enhance the Voc. On the
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other hand, the effective way to prevent π-aggregation and charge recombination is

still the incorporation of the alkyl chain into the π-bridge. Similar results have been

reported by other group [45].

Fig. 6. J−V curves of the DSSCs based on DT1-DT4.

Chenodeoxycholic acid (CDCA) has been verified that it can hinder the
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intermolecular aggregations of dyes on TiO2 films, and then improve the DSSCs

performance [46]. Thus, the performances of the DSSCs of DT1-DT4 in the presence

of 1 mM CDCA have been studied (Fig. 7), and the corresponding data are depicted in

Table 5. Upon coadsorption of CDCA, the short-circuit photocurrent and power

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conversion efficiency of DT1-DT3 are improved significantly. The remarkable

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enhancements of the DSSC performances are attributed to the hampering of dye

aggregation, which improves the electron injection efficiency [47]. However, after

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addition of CDCA, the Jsc and η values of DT4 decreased. A possible reason is that

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there is no or less aggregation of DT4 on TiO2 film, but the dye loading amount of the
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dye on the TiO2 surface is minished, resulting in a loss of active light-harvesting. This

result indicates that DT4 with two branched alkyl chains (2-ethylhexyl groups) can
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effectively suppress intermolecular interactions and inhibit dye aggregation on the

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TiO2 surface. After addition of CDCA, the Voc values of DSSCs based on DT1 and
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DT2 are improved, indicating that the charge recombination process is effectively

restrained with a content of CDCA. However, the Voc values of DT3 and DT4
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decrease, which might be ascribed to that the adsorption of excess CDCA leaves
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protons on the TiO2 films and then lead to a loss in Voc [48,49].
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Fig. 7. J−V curves of the DSSCs based on DT1-DT4 with 1 mM CDCA as

coadsorbent

Table 5. Photovoltaic performance parameters of the DSSCs based on DT1-DT4 with

CDCA.

Electrochemical impedance spectroscopy (EIS) analysis was carried to elucidate

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the interfacial charge recombination process in the dark. The Nyquist plots for the

DSSCs based on DT1-DT4 are shown in Fig. 8. The four sensitizers all exhibit two

semicircles. The smaller semicircle at higher frequencies accords to the charge

transfer at the Pt/electrolyte interface, while the larger semicircle at lower frequencies

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relates to the charge transfer at the TiO2/dye/electrolyte interface [33,50]. The charge

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recombination resistance at the TiO2 surface (Rrec) from a range of lower frequencies

can be deduced by fitting curves using Z-view software. Generally, a smaller Rrec

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value indicates a faster charge recombination and a larger dark current [51]. The Rrec

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values for the DSSCs increase in the order of DT2 (179 Ω) < DT3 (203 Ω) < DT1
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(206 Ω) < DT4 (218 Ω). The trend observed here is consistent with the order of the

Voc value, DT2 (656 mV) < DT3 (694 mV) < DT1 (696 mV) < DT4 (723 mV). In the
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Bode phase plots (Fig. 9), the peak of the middle frequency (left) is related to the
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electron lifetime, and a lower frequency of the peak corresponds to a longer electron
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lifetime. The electron lifetime (τn) can be estimated from τn = 1/(2πfp), where fp is the

peak frequency in lower frequency region [52]. As shown in Fig. 9, the value of the
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middle frequency peak decreases in the order of DT2 > DT3 > DT1 > DT4. Thus, the
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electron lifetimes of the four dyes increase in the order of DT2 (12.7 ms) < DT3 (16.0
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ms) < DT1 (16.2 ms) < DT4 (31.6 ms). Obviously, these data further support the

order of the Voc value of the DSSCs based on DT1-DT4. Hence, DT4 with two

branched alkyl chains in the π-spacer possesses more efficient suppression of charge

recombination of the injection electron with I3- in the electrolyte than the other three

dyes.
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Fig. 8. EIS Nyquist plots for the DSSCs based on DT1-DT4 under dark.

Fig. 9. EIS Bode plots for the DSSCs based on DT1-DT4 under dark.

3. Conclusion

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In summary, four novel metal-free organic dyes DT1-DT4 containing a DTBT unit

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as the π-spacer were successful synthesized and utilized for DSSCs. The results show

that the four dyes have high molar extinction coefficient (5.9–7.0 × 104 M-1 cm-1) and

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broad spectral absorption. They show effective electron separation from HOMO

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levels to LUMO levels, which is confirmed by DFT and TD-DFT calculations. The
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different electron donors affect the solar cell performance. For DT1-DT3, when the

electron donor from triphenylamine was changed to dihexyloxyl substituted

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triphenylamine and dihexyloxylphenyl substituted triphenylamine, the short-circuit

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currents and power conversion efficiencies increased. Moreover, it is found that the
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different alkyl chain groups on the DTBT unit greatly influence the photovoltaic

performance of the dyes. The branched alkyl chains (2-ethylhexyl chains) are superior
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to the linear alkyl chains (hexyl chains) in suppressing intermolecular dye aggregation
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and restricting charge recombination. Under standard global AM 1.5G solar light
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illumination conditions, the DSSC based on DT4 yields the highest overall conversion

efficiency of 8.05%, which means that the DTBT-based organic sensitizer is a

promising candidate for efficient DSSCs.

Acknowledgments
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We are grateful to the National Natural Science Foundation of China (21272079),

the Science and Technology Planning Project of Guangdong Province, China

(2013B010405003), and the Fundamental Research Funds for the Central Universities

(2014ZP0008).

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Table 1. Photophysical and electrochemical parameters of DT1-DT4.

Dye λmax/nma λmax on λ(nm)b HOMOc LUMOd(vs.NHE) E0-0e
/(ε/M-1 cm-1) TiO2(nm) (vs.NHE) (V) (eV)
(V)
DT1 548(63779) 477 607 0.89 –1.15 2.04

DT2 555(59430) 471 603 0.78 –1.28 2.06

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DT3 551(70802) 466 604 0.88 –1.17 2.05

DT4 548(59522) 491 609 0.88 –1.16 2.04

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a
Absorption maximum of dyes measured in CH2Cl2 with concentration 2×10-5 M. ε:

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Molar extinction coefficient at λmax.
b
λ intersection obtained from the cross point of normalized absorption and emission
spectra in CH2Cl2 solution.
c
HOMO of the dyes by cyclic voltammetry in 0.1 M TBAPF6 in dry MeCN solutions

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as supporting electrolyte, Ag/AgCl as the reference electrode and Pt wire as counter
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electrode, scanning rate of 50 mV s-1.
d
LUMO was calculated by HOMO – E0-0.
e
E0-0 = 1240/λ intersection.
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Table 2. Optimized structures and electron distributions in HOMO and LUMO levels
of DT1-DT4.
Dyes Optimized structure HOMO LUMO

DT1

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DT2

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DT3
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DT4
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Table 3. Calculated TD-DFT Wavelengths, Excitation energies (eV), and

Composition in terms of Molecular Orbital Contributions of the dyes DT1-DT4 with
Oscillator Strengths (f) larger than 0.5.
Dye Wavelength E Compositiona f
(eV)
DT1 509.1 2.44 H L: 83.9%, H–1 L: 11.4% 2.0788

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347.9 3.56 H L+1 83.9% 0.6038
DT2 517.7 2.39 H L:77.0%, H–1 L: 18.2% 2.0439
352.3 3.52 H L+1 82.5% 0.6563

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DT3 511.6 2.42 H L:73.2%, H–1 L: 21.1% 2.1677
355.4 3.49 H L+1 80.5% 0.7383
DT4 508.8 2.44 H L:83.7%, H–1 L:11.4% 2.0424

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348.5 3.56 H L+1 83.7% 0.5779
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H = HOMO, L = LUMO, H–1 = HOMO–1, L = LUMO, L+1 = LUMO+1.

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Table 4. Photovoltaic performance parameters of the DSSCs based on DT1-DT4.

Dye Jsc Voc η FF Dye loading amount
(mA cm-2) (mV) (%) (mol cm-2)

DT1 11.20 696 5.01 0.64 2.86 × 10-7

DT2 12.19 656 5.27 0.66 2.52 × 10-7

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DT3 12.81 694 5.86 0.66 1.68 × 10-7
DT4 16.35 723 8.05 0.68 1.70 × 10-7

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Table 5. Photovoltaic performance parameters of the DSSCs based on DT1-DT4 with

CDCA.
Dye Jsc Voc η FF
(mA cm-2) (mV) (%)

DT1 15.03 735 7.50 0.68

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DT2 16.06 700 7.32 0.65
DT3 13.85 689 6.47 0.68

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DT4 15.95 705 7.34 0.65

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Figure Captions

Scheme 1. Synthetic route of DT1-DT4. (a) Fum. HNO3, conc. H2SO4; (b)
tributyl(thiophen-2-yl)stannane, Pd(PPh3)2Cl2, THF; (c) (1) o-DCB, PPh3; (2)
1-bromohexane, KOH, KI, DMSO; (d) DMF, POCl3, 1,2-dichloroethane; (e) NBS,
THF; (f) (4-(diphenylamino)phenyl)boronic acid or 4-(hexyloxy)-N-(4-(hexyloxy)-

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phenyl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl) aniline or 4'-(hex-
yloxy)-N-(4'-(hexyloxy)-[1,1'-biphenyl]-4-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxabo

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rolan-2-yl)phenyl)[1,1'-biphenyl]-4-amine, Pd(PPh3)4, K2CO3, THF; (g) (1) tert-butyl

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2-cyanoacetate, ammonium acetate, acetic acid, toluene; (2) trifluoroacetic acid; (h) (1)
o-DCB, PPh3; (2) 2-ethylhexyl bromide, KOH, KI, DMSO.

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Fig. 1. Chemical structure of the dyes DT1-DT4.
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Fig. 2. Absorption spectra (a) and emission spectra (b) of DT1-DT4 in CH2Cl2

solutions.
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Fig. 3. Absorption spectra of DT1-DT4 on TiO2 films.

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Fig. 4. Cyclic voltammograms of DT1-DT4.

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Fig. 5. IPCE spectra of the DSSCs based on DT1-DT4.

Fig. 6. J−V curves of the DSSCs based on DT1-DT4.

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Fig. 7. J−V curves of the DSSCs based on DT1-DT4 with 1 mM CDCA as

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coadsorbent
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Fig. 8. EIS Nyquist plots for the DSSCs based on DT1-DT4 under dark.

Fig. 9. EIS Bode plots for the DSSCs based on DT1-DT4 under dark.
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Scheme 1. Synthetic route of DT1-DT4. (a) Fum. HNO3, conc. H2SO4; (b)
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tributyl(thiophen-2-yl)stannane, Pd(PPh3)2Cl2, THF; (c) (1) o-DCB, PPh3; (2)

1-bromohexane, KOH, KI, DMSO; (d) DMF, POCl3, 1,2-dichloroethane; (e) NBS,
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THF; (f) (4-(diphenylamino)phenyl)boronic acid or 4-(hexyloxy)-N-(4-(hexyl-oxy)-

phenyl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl) aniline or 4'-
(hexyloxy)-N-(4'-(hexyloxy)-[1,1'-biphenyl]-4-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-
dioxaborolan-2-yl)phenyl)[1,1'-biphenyl]-4-amine, Pd(PPh3)4, K2CO3, THF; (g) (1)
tert-butyl 2-cyanoacetate, ammonium acetate, acetic acid, toluene; (2) trifluoroacetic
acid; (h) (1) o-DCB, PPh3; (2) 2-ethylhexyl bromide, KOH, KI, DMSO.
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Graphical Abstract

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Highlights
1、Novel dithienopyrrolobenzotriazole-based organic dyes were synthesized.

2、The reported four dyes show high molar extinction coefficient.

3、The donors and alkyl chains greatly influence the photovoltaic performance.

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4、DT4 sensitized solar cell obtained a high power conversion efficiency of 8%.

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