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Y.-H. Chiu et al. / Dyes and Pigments 136 (2017) 761e772
gel column chromatograph eluted with EA/hexane (1:10). Orange
solid of 7a was obtained in 82% yield (5.5 g, 6.55 mmol). Spec-
troscpoic data for 7a. dH (400 MHz, CDCl3) 7.54e7.58 (m, 5H),
7.28e7.31 (m, 5H), 7.21e7.24 (m, 5H), 7.09e7.12 (m, 2H), 7.05 (s,
2H), 6.97 (d, 2H, J ¼ 15.92 Hz), 6.83 (d, 4H, J ¼ 7.6 Hz), 6.76 (d, 2H,
J ¼ 7.68 Hz), 6.70 (d, 2H, J ¼ 7.8 Hz), 6.65 (d, 2H, J ¼ 7.72 Hz), 6.62 (d,
2H, J ¼ 7.52 Hz), 3.19e3.24 (m, 2H), 2.72e2.85 (m, 9H), 2.58e2.66
(m, 4H), 2.04e2.22 (m, 9H). dC (100 MHz, CDCl3) 146.7, 146.4, 144.2,
139.0, 138.3, 136.3, 135.0, 133.1, 132.0, 129.9, 129.5, 129.1, 128.0,
127.9, 127.4, 127.3, 126.8, 126.2, 124.4, 124.2, 124.1, 122.4, 36.0, 35.9,
35.4, 31.6, 29.6, 27.9. MS (FAB, 70 eV): m/z (relative intensity) 847
(Mþ, 100); HRMS calcd for C62H57NS: 847.4212, found 847.4218.
purified by silica gel column chromatograph eluted with CH2Cl2/
acetic acid (19/1). The dark red solid was isolated in 50% yield
(592 mg, 0.58 mmol) Spectroscopic data of H-1: dH (400 MHz,
DMSO-d6) 8.43 (s, 1H), 7.95 (d, 1H, J ¼ 3.56 Hz), 7.74 (d, 2H,
J ¼ 8.56 Hz), 7.63 (d,1H, J ¼ 3.72 Hz), 7.57 (d, 5H, J ¼ 8.44 Hz), 7.17 (d,
5H, J ¼ 8.52 Hz), 6.86e6.89 (m, 4H), 6.66e6.78 (m, 11H), 3.12e3.18
(m, 2H), 2.63e2.68 (m, 15H), 2.30e2.31 (m, 1H), 1.98e2.03 (m, 6H);
dC (100 MHz, DMSO-d6) 146.7, 145.2, 140.4, 138.9, 138.3, 138.2, 134.1,
133.1,131.0,130.6,130.3,129.8,129.4,128.6,128.1,127.3,125.1,124.4,
122.0, 118.2, 117.4, 92.4, 89.9, 35.6, 35.3, 34.1, 29.4, 28.1, 26.1; MS
(FAB, 70 eV): m/z (relative intensity) 1020 (Mþ, 100); HRMS calcd
for C70H56N2O2S: 1020.3783, found 1020.3778.
4.1.9. 4-((E)-Styryl)-N-(4-((E)-styryl)phenyl)-N-(4-(thiophen-2-yl)
phenyl)aniline (7b)
4.1.13. (E)-3-(5'-(4-(Bis(4-(phenylethynyl)phenyl)amino)phenyl)-
[2,2'-bithiophen]-5-yl)-2-cyanoacrylic acid (H-2)
Compound 7b was synthesized according to the same procedure
as that of 7a. Orange solid of 7b was obtained in 88% yield. dH
(400 MHz, CDCl3) 7.52e7.55 (m, 6H), 7.45 (d, 4H, J ¼ 8.56 Hz), 7.38
(t, 4H, J ¼ 7.8 Hz), 7.25e7.29 (m, 5H), 7.13e7.17 (m, 6H), 7.07e7.10
(m, 4H). dC (100 MHz, CDCl3) 146.7, 146.6, 144.1, 137.5, 132.2, 129.2,
128.6, 128.0, 127.4, 127.3, 126.8, 126.3, 124.4, 124.2, 122.4. MS (FAB,
70 eV): m/z (relative intensity) 531 (Mþ, 100); HRMS calcd for
Compound H-2 was synthesized according to the same pro-
cedure as that of H-1. Red solid of H-2 was obtained in 76%. dH
(400 MHz, THF-d8) 8.36 (s, 1H), 7.81 (d, 1H, J ¼ 4.04 Hz), 7.68 (d, 2H,
J ¼ 8.68 Hz), 7.50e7.53 (m, 5H), 7.47 (d, 4H, J ¼ 8.6 Hz), 7.42 (t, 2H,
J ¼ 4.36 Hz), 7.34e7.39 (m, 6H), 7.18 (d, 2H, J ¼ 8.68 Hz), 7.14 (d, 4H,
J ¼ 8.64 Hz); dC (100 MHz, THF-d8) 163.0, 146.9, 146.8, 146.3, 145.5,
145.3, 139.2, 134.5, 134.4, 132.6, 131.2, 129.0, 128.2, 127.9, 127.5,
126.7, 124.9, 124.1, 124.0, 123.8, 123.5, 117.9, 115.6, 98.6, 89.0, 88.9;
MS (FAB, 70 eV): m/z (relative intensity) 704 (Mþ, 100); HRMS calcd
for C46H28N2O2S2: 704.1592, found 704.1590.
C
38H29NS: 531.2021, found 531.2024.
4.1.10. 5'-(4-(Bis(4-((E)-2-(1,5(1,4)-dibenzenacyclooctaphane-12-
yl)vinyl)phenyl)amino)phenyl)-[2,2'-bithiophene]-5-carbaldehyde
(8a)
4.1.14. (E)-3-(5'-(4-(Bis(4-((E)-2-(1,5(1,4)-
Compound 8a was synthesized according to the same procedure
as that of 5a. Orange solid of 8a was obtained in 75% yield. dH
(400 MHz, CDCl3) 9.89 (s, 1H), 7.69 (d, 1H, J ¼ 3.96 Hz), 7.57e7.61
(m, 6H), 7.37 (d,1H, J ¼ 3.88 Hz), 7.34 (d, 2H, J ¼ 16.08 Hz), 7.24e7.29
(m, 8H), 7.09 (s, 2H), 7.01 (d, 2H, J ¼ 16.04 Hz), 6.86 (d, 4H,
J ¼ 7.72 Hz), 6.79 (d, 2H, J ¼ 7.72 Hz), 6.74 (d, 2H, J ¼ 7.84 Hz),
6.64e6.69 (m, 4H), 3.22e3.27 (m, 2H), 2.81e2.90 (m, 9H),
2.62e2.69 (m, 4H), 2.14e2.26 (m, 7H), 2.04e2.09 (m, 2H). dC
(100 MHz, CDCl3) 182.3, 147.6, 147.3, 146.2, 146.1, 141.4, 139.0, 138.3,
137.4, 136.4, 135.0, 134.3, 133.5, 132.0, 129.9, 129.6, 129.1, 127.8,
127.6,127.5,127.4,127.3,126.7,126.5,126.1,124.8,123.8,123.7,123.4,
36.0, 35.9, 35.5, 33.6, 29.7, 28.0. MS (FAB, 70 eV): m/z (relative in-
tensity) 957 (Mþ, 100); HRMS calcd for C67H59NOS2: 957.4038,
found 957.4039.
dibenzenacyclooctaphane-12-yl)vinyl)phenyl)amino)phenyl)-[2,2'-
bithiophen]-5-yl)-2-cyanoacrylic acid (H-3)
Compound H-3 was synthesized according to the same pro-
cedure as that of H-1. Red solid of H-3 was obtained in 72%. dH
(400 MHz, THF-d8) 8.32 (s, 1H), 7.78 (d, 1H, J ¼ 4.08 Hz), 7.67 (d, 2H,
J ¼ 8.72 Hz), 7.63 (d, 4H, J ¼ 8.6 Hz), 7.51 (d, 1H, J ¼ 3.88 Hz), 7.42 (d,
2H, J ¼ 3.56 Hz), 7.38 (d, 2H, J ¼ 15.92 Hz), 7.22 (d, 6H, J ¼ 8.56 Hz),
7.10 (s, 2H), 7.07 (d, 2H, J ¼ 15.92 Hz), 6.80 (d, 4H, J ¼ 8.0 Hz),
6.70e6.74 (m, 4H), 6.61e6.64 (m, 4H), 3.25e3.28 (m, 2H),
2.76e2.85 (m, 13H), 2.15e2.26 (m, 7H), 2.00e2.06 (m, 2H); dC
(100 MHz, THF-d8) 163.6, 147.6, 146.3, 145.6, 144.2, 138.7, 138.2,
138.0,137.9, 136.2,135.1,134.8,134.2,133.7, 131.8, 129.7, 128.9,127.8,
127.7, 127.4, 127.2, 127.0, 126.4, 126.2, 125.9, 124.6, 123.8, 123.6,
123.5, 116.1, 35.9, 35.7, 35.3, 33.4, 29.6, 29.5, 27.9; MS (FAB, 70 eV):
m/z (relative intensity) 1024 (Mþ, 100); HRMS calcd for
4.1.11. 5'-(4-(Bis(4-((E)-styryl)phenyl)amino)phenyl)-[2,2'-
bithiophene]-5-carbaldehyde (8b)
C70H60N2O2S2: 1024.4096, found 1024.4092.
Compound 8b was synthesized according to the same procedure
as that of 5a. Red solid of 8b was obtained in 77% yield. dH
(400 MHz, CDCl3) 9.88 (s,1H), 7.69 (d,1H, J ¼ 3.96 Hz), 7.51e7.54 (m,
6H), 7.46 (d, 4H, J ¼ 8.6 Hz), 7.38 (t, 4H, J ¼ 7.8 Hz), 7.34 (d, 1H,
J ¼ 3.92 Hz), 7.26e7.29 (m, 4H), 7.22 (d, 1H, J ¼ 3.88 Hz), 7.14e7.16
(m, 6H), 7.08 (d, 3H, J ¼ 6.4 Hz). dC (100 MHz, CDCl3) 182.4, 147.4,
147.3, 146.4, 146.0, 141.3, 137.5, 137.4, 134.3, 132.6, 128.7, 127.9, 127.8,
127.7, 127.5, 127.4, 127.2, 126.7, 126.3, 124.5, 123.9, 123.8, 123.4. MS
(FAB, 70 eV): m/z (relative intensity) 641 (Mþ, 100); HRMS calcd for
4.1.15. (E)-3-(5'-(4-(Bis(4-((E)-styryl)phenyl)amino)phenyl)-[2,2'-
bithiophen]-5-yl)-2-cyanoacrylic acid (H-4)
Compound H-4 was synthesized according to the same pro-
cedure as that of H-1. Red solid of H-4 was obtained in 83%. dH
(400 MHz, THF-d8) 8.36 (s, 1H), 7.82 (d, 1H, J ¼ 4.08 Hz), 7.64 (d, 2H,
J ¼ 8.64 Hz), 7.52e7.57 (m, 9H), 7.42 (t, 2H, J ¼ 3.92 Hz), 7.34 (t, 4H,
J ¼ 7.76 Hz), 7.17e7.24 (m, 7H), 7.13e7.16 (m, 5H); dC (100 MHz, THF-
d8) 163.0, 147.5, 146.4, 145.9, 145.3, 139.2, 137.7, 134.4, 134.0, 132.9,
128.3,127.9, 127.7, 127.5, 127.4,127.0, 126.4,126.1, 124.3,123.9,123.7,
123.6, 115.6, 98.5; MS (FAB, 70 eV): m/z (relative intensity) 708 (Mþ,
100); HRMS calcd for C46H32N2O2S2: 708.1905, found 708.1900.
C
43H31NOS2: 641.1847, found 641.1844.
4.1.12. (E)-3-(5'-(4-(Bis(4-(1,5(1,4)-dibenzenacyclooctaphane-12-
ylethynyl)phenyl)amino)phenyl)-[2,2'-bithiophen]-5-yl)-2-
cyanoacrylic acid (H-1)
4.2. Fabrication of DSSCs and characterization of DSSCs
A mixture of 5a (110 mg, 1.16 mmol), cyanoacetic acid (118 mg,
1.39 mmol), and ammonium acetate (27 mg, 0.35 mmol) were
placed in a three-necked flask in acetic acid under a nitrogen at-
mosphere with heating 100 ꢂC for 12 h. After cooling, the reaction
was quenched by adding water, and extracted with CH2Cl2. The
organic layer was dried over anhydrous MgSO4, and concentrated
under reduced pressure to give the crude product. The product was
The FTO conducting glass (FTO glass, fluorine doped tin oxide
over-layer, transmission >90% in the visible, sheet resistance 7
U
squareꢀ1), titania-oxide pastes of Ti-Nanoxide T/SP and Ti-
Nanoxide R/SP were purchased from Solaronix. A thin film of TiO2
(16e18 m
m) was coated on a 0.28 cm2 FTO glass substrate. It was
immersed in a THF solution containing 3 ꢁ 10ꢀ4 M dye sensitizers
for at least 12 h, then rinsed with anhydrous acetonitrile and dried.