M. Matsui et al. / Dyes and Pigments 91 (2011) 145e152
151
d
¼ 2.58 (quin, J ¼ 6.9 Hz, 2H), 2.90 (t, J ¼ 6.9 Hz, 2H), 2.95 (t,
The organic layer was separated, washed with water, and dried over
anhydrous sodium sulfate. The product was isolated by column
chromatography (SiO2, CHCl3). Yield 53%; mp 135e138 ꢀC; 1H NMR
J ¼ 6.9 Hz, 2H), 7.36 (t, J ¼ 8.3 Hz, 1H), 7.47 (t, J ¼ 8.3 Hz, 1H), 7.48
(d, J ¼ 8.7 Hz,1H), 7.57 (d, J ¼ 8.7 Hz,1H), 7.89 (d, J ¼ 8.3 Hz,1H), 7.92
(d, J ¼ 8.3 Hz, 1H); EIMS (70 eV) m/z (rel intensity) 207 (Mþ, 100),
180 (31), 103 (20).
(CDCl3)
d
¼ 1.26e1.32 (m, 1H), 1.56e1.58 (m, 1H), 1.79e1.86 (m, 3H),
2.01e2.07 (m, 1H), 4.07e4.10 (m, 1H), 4.62e4.65 (m, 1H), 6.93 (d,
J ¼ 7.6 Hz, 2H), 6.98 (d, J ¼ 7.6 Hz, 2H), 7.10 (s,1H), 7.15e7.16 (m, 3H),
7.21e7.35 (m, 7H), 7.40 (t, J ¼ 7.6 Hz, 2H), 7.50 (t, J ¼ 7.6 Hz,1H), 8.06
(d, J ¼ 8.9 Hz, 1H), 8.38 (s, 1H), 8.85 (s, 1H); FABHRMS m/z 559.2390
(MHþ), calcd for C39H31N2O2 559.2386.
4.4. Synthesis of 6b,7,8,9,9a,10-hexahydrobenzo[g]cyclopenta[b]
indole (4)
To an acetic acid suspension (5 ml) of 7,8,9,10-tetrahydrobenzo
[g]cyclopenta[b]indole 3 (212 mg, 1.02 mmol) was added sodium
borohydride (80 mg, 2.12 mmol) below 35 ꢀC. The mixture was
stirred one day at room temperature. After the reaction was
completed, water was added. The product was extracted with
dichloromethane and purified by silica gel column chromatography
4.8. Synthesis of 12
To acetic acid (8 ml) were added 7 (254 mg, 0.52 mmol) and 8
(103 mg, 0.54 mmol). The mixture was heated to 120 ꢀC. Then, to
the mixture was added ammonium acetate (18 mg, 0.23 mmol). The
mixture was heated at 120 ꢀC for 90 min. After the reaction was
completed, to the mixture was added water. The resulting precip-
itate was filtered and washed with water and methanol. The
product was isolated by column chromatography (SiO2, CHCl3).
(CH2Cl2:C6H14 ¼ 5:1). Yield 68%; oil; 1H NMR (CDCl3)
¼ 1.26e1.38
d
(m, 1H), 1.56e1.59 (m, 1H), 1.67e1.77 (m, 3H), 1.86e1.95 (m, 1H),
3.83e3.87 (m, 1H), 4.42e4.44 (m, 1H), 6.21 (br s, 1H), 7.02 (d,
J ¼ 7.8 Hz, 1H), 7.14 (d, J ¼ 7.8 Hz, 1H), 7.24e7.30 (m, 2H), 7.65e7.68
(m,1H), 7.71e7.73 (m,1H); EIMS (70 eV) m/z (rel intensity) 209 (Mþ,
45), 180 (100).
Yield 34%; mp 159e162 ꢀC; 1H NMR (CDCl3)
d
¼ 1.30e1.34 (m, 1H),
1.56e1.61 (m, 1H), 1.80e1.89 (m, 3H), 2.04e2.11 (m, 1H), 4.12e4.14
(m, 1H), 4.58e4.61 (m, 1H), 6.89 (d, J ¼ 7.9 Hz, 2H), 6.97 (d,
J ¼ 7.6 Hz, 2H), 7.08 (s, 1H), 7.15e7.19 (m, 3H), 7.24e7.41 (m, 9H),
7.52 (t, J ¼ 7.9 Hz, 1H), 7.58 (s, 1H), 8.18 (d, J ¼ 8.2 Hz, 1H), 8.44
(s, 1H); FABHRMS m/z 665.1917 (MHþ), calcd for C41H33N2O3S2
665.1933.
4.5. Synthesis of 10-[4-(2,2-diphenylethenyl)phenyl]-6b,-
7,8,9,9a,10-hexahydrobenzo[g]cyclopenta[b]- indole (6)
To xylene solution (10 ml) of 6b,7,8,9,9a,10-tetrahydrobenzo[g]
cyclopenta[b]indole (731 mg, 2.32 mmol) were added 1-bromo-4-
(2,2-diphenylethenyl)benzene (5) (476 mg, 2.27 mmol), potassium
tert.-butoxide (310 mg, 2.76 mmol), palladium acetate (10 mg,
0.05 mmol), and tri-t-butylphosphine (13 mg, 0.06 mmol). The
mixture was heated at 120 ꢀC for 16 h. After the reaction was
completed, the product was filtered using celite. The product was
washed with 2 N hydrochloric acid and purified by silica gel column
chromatography (CH2Cl2 : C6H14 ¼ 2:1). Yield 69%; mp 79e82 ꢀC; 1H
4.9. Synthesis of 13
To acetic acid (8 ml) were added 7 (0.230 g, 0.47 mmol) and 9
(0.151 g, 0.47 mmol). The mixture was heated to 120 ꢀC. Then, to the
mixture was added ammonium acetate (0.021 g, 0.27 mmol). The
mixture was heated at 120 ꢀC for 90 min. After the reaction was
completed, to the mixture was added water. The resulting precipi-
tate was filtered and washed with water and methanol. The product
was isolated by column chromatography (SiO2, CHCl3). Yield 28%;
NMR (CDCl3)
d
¼ 1.17e1.26 (m,1H),1.49e1.56 (m,1H),1.72e1.75, (m,
1H), 1.80e1.87 (m, 1H), 1.96e2.05 (m, 2H), 4.08e4.11 (m, 1H),
4.29e4.32 (m,1H), 6.64 (d, J ¼ 8.7 Hz, 2H), 6.85 (d, J ¼ 8.7 Hz, 2H), 7.01
(s, 2H), 7.07e7.41 (m, 14H), 7.47 (d, J ¼ 8.2 Hz,1H), 7.81 (d, J ¼ 8.2 Hz,
1H); EIMS (70 eV) m/z (rel intensity) 463 (Mþ, 100), 434 (23).
mp 226e228 ꢀC; 1H NMR (CDCl3)
d
¼ 1.14 (t, J ¼ 6.8 Hz, 3H),
1.30e1.33 (m, 1H), 1.60e1.62 (m, 1H), 1.85e1.91 (m, 3H), 2.05e2.17
(m, 1H), 4.02 (q, J ¼ 6.8 Hz, 2H), 4.15e4.19 (m, 1H), 4.56e4.61 (m,
1H), 4.81 (s, 2H), 6.87 (d, J ¼ 8.0 Hz, 2H), 6.96 (d, J ¼ 8.0 Hz, 2H), 7.08
(s,1H), 7.15e7.42 (m,12H), 7.50 (t, J ¼ 7.3 Hz,1H), 7.69 (s,1H), 8.15 (d,
J ¼ 8.7 Hz,1H), 8.44 (s,1H); FABHRMS m/z 792.1974 (MHþ), calcd for
C46H38N3O4S3 792.2024.
4.6. Synthesis of 10-[4-(2,2-diphenylethenyl)phenyl]-
6b,7,8,9,9a,10-hexahydrobenzo[g]- cyclopenta[b]indole-5-
carbaldehyde
To DMF (1 ml) was added phosphoryl chloride (252 mg,1.64 mmol)
at 10 ꢀC. The mixture was stirred for 30 min. To this mixture was added
a DMF solution of 10-[4-(2,2-diphenylethenyl)phenyl]-6b,7,8,9,9a,10-
hexahydrobenzo[g]cyclopenta[b]indole 6(327 mg, 0.71 mmol) below
20 ꢀC. The mixture was stirred for 2 h. After the reaction was
completed, the mixture was poured onto ice and neutralized with
aqueous sodium hydroxide. The product was extracted with
dichloromethane and purified by silica gel column chromatography
4.10. Preparation of zinc oxide solar cell
An aqueous potassium chloride solution (300 ml, 0.1 mol dmꢁ3
)
was electrolyzed at ꢁ1.0 V vs. SCE with bubbling an oxygen gas at
70 ꢀC for 30 min. Platinum was used as a counter electrode. To the
pre-electrolyzed film was added an aqueous solution of zinc chlo-
ride (5 mmol dmꢁ3). Then, the film was electro-deposited again in
the solution at ꢁ1.0 V vs. SCE at 70 ꢀC for 20 min with bubbling an
oxygen gas. To the electro-deposited film was added an aqueous
(CH2Cl2). Yield 63%; mp 193e195 ꢀC; 1H NMR (CDCl3)
d
¼ 1.26e1.32
(m, 1H), 1.57e1.59 (m, 1H), 1.82e1.88, (m, 3H), 2.01e2.08 (m, 1H),
4.07e4.11 (m, 1H), 4.57e4.62 (m, 1H), 6.91 (d, J ¼ 8.2 Hz, 2H), 6.98 (d,
J ¼ 8.2 Hz, 2H), 7.09 (s, 1H), 7.15e7.42 (m, 12H), 7.51 (t, J ¼ 8.3 Hz, 1H),
7.92 (s, 1H), 9.19 (d, J ¼ 8.3 Hz, 1H), 10.05 (s, 1H); EIMS (70 eV) m/z (rel
intensity) 491 (Mþ, 100), 462 (16).
solution of Eosin Y (50 m
mol dmꢁ3). The film was electro-deposited
at ꢁ1.0 V vs. SCE at 70 ꢀC for 30 min with bubbling an oxygen gas.
The film was kept in a diluted aqueous potassium hydroxide solu-
tion (pH 10.5) for 24 h to remove adsorbed Eosin Y. The film was
dried at 100 ꢀC for 1 h. The thin film was immersed in a chloroform
solution of dye (1 ꢂ 10ꢁ4 mol dmꢁ3) and kept at ambient temper-
ature for 1 h to adsorb dyes 11,12, and 13. In the cases of D131, D102,
and D149, the film was immersed in an acetonitrile-tert.-butyl
alcohol 1:1 mixed solution (5 ꢂ 10ꢁ4 mol dmꢁ3). Then, the film was
washed with chloroform. The films were dried under an air
atmosphere at ambient temperature. The film was used as the
working electrode. Platinum spattered film was used as a counter
4.7. Synthesis of 11
To acetonitrile (5 ml) were added 7 (254 mg, 0.52 mmol), cya-
noacetic acid 8 (121 mg, 1.42 mmol), and piperidine (57 mg,
0.67 mmol). The mixture was refluxed for 120 ꢀC. Then, to the
mixture was added chloroform and 2 N aqueous hydrochloric acid.