Lee et al.
Carbazole-Functionalized Organic Photosensitizer for Dye-Sensitized Solar Cells
poured into methylene chloride and washed with aqueous
2.3.7. Synthesis of Compound 6
phosphoric acid (2.0 M in water). The organic phase was
purified by column chromatography on silica gel using
methylene chloride and THF (1:5, v/v) as an eluent. Yield
A THF solution (40 mL) of 5 (1.50 g, 2.49 mmol) was
added into a THF solution of potassium tert-butoxide
(2.98 mL, 2.98 mmol) and methyl triphenyl phospho-
nium iodide (1.21 g, 2.30 mmol). The solution was then
stirred at room temperature for 2 h under nitrogen. After
removal of the solvent, the mixture was poured into methy-
lene chloride and washed with distilled water. The organic
layer was purified by column chromatography on silica
gel using n-hexane as an eluent. Yield (1.21 g, 81%).
mp 177–178 C. H NMR (400 MHz, DMSO-d6) ꢅ 5.25
(d, J = 11.0 Hz, 1 H, –CH CH2), 5.73 (d, J = 17.6 Hz,
1 H, –CH CH2), 6.74 (dd, J = 11.0, 17.6 Hz, 1 H, –
CH CH2), 7.30 (d, J = 8.8 Hz, 2 H, –Ph–CHO), 7.32
(t, J = 7.7 Hz, 4 H, –Ph–carbazole), 7.46 (t, J = 7.7 Hz,
–Ph–carbazole), 7.49 (d, J = 8.8 Hz, 4 H, –Ph–carbazole),
7.51 (d, J = 7.7 Hz, 4 H, –Ph–carbazole), 7.61 (d, J =
8.8 Hz, 4 H, –Ph–carbazole), 7.85 (d, J = 8.8 Hz, 2 H, –
Ph–CH CH2), 8.17 (d, J = 7.7 Hz, 4 H, –Ph–carbazole);
13C NMR (100.64 MHz, DMSO-d6) ꢅ 109.48, 113.13,
119.69, 120.21, 122.40, 124.40, 124.54, 125.91, 127.40,
127.76, 131.36, 132.65, 135.74, 140.09, 145.76, 146.11.
ꢁ
1
(343 mg, 35%). mp 283–285 C. H NMR (400 MHz,
DMSO-d6) ꢅ 7.10 (d, J = 16.5 Hz, 1 H, –CH CH–),
7.30 (t, J = 7.7 Hz, 4 H, –Ph–carbazole), 7.46 (t, J =
7.7 Hz, 4 H, –Ph–carbazole), 7.49 (d, J = 8.8 Hz, 4 H, –
N–Ph–carbazole), 7.51 (d, J = 16.5 Hz, 1 H, –CH CH–),
7.53 (d, J = 8.8 Hz, 4 H, –N–Ph–carbazole), 7.57 (d,
ꢁ
1
J = 8.8 Hz, 2 H,
CH–Ph–N–), 7.63 (d, J = 7.7 Hz,
4 H, –Ph–carbazole), 7.71 (d, J = 7.3 Hz, 2 H, CH–Ph–
CHO), 7.79 (d, J = 7.3 Hz, 2 H, CH–Ph–N–), 8.05 (d,
J = 8.8 Hz, 2 H, CH–Ph–N–), 8.25 (d, J = 7.7 Hz, 4 H,
–Ph–carbazole), 8.27 (s, 1 H, CH–Ph–CH CH–); 13C
NMR (100.64 MHz, DMSO-d6) ꢅ 102.50, 109.50, 116.22,
119.71, 120.22, 122.42, 123.83, 124.06, 124.96, 125.92,
126.65, 127.80, 128.24, 130.06, 130.97, 131.10, 131.63,
131.68, 140.06, 141.85, 145.54, 146.65, 153.05, 163.08;
MS (MALD-TOF) calcd 772.89, found 772.64 [m+H]+.
2.3.10. Synthesis of Compound 8
A DMAc solution (30 mL) of 6 (1.0 g, 1.66 mmol),
4-iodo-2,5-dimethoxybenzaldehyde (0.63 g, 2.16 mmol),
sodium carbonate (0.53 g, 4.99 mmol), 2,6-di-tert-
butyl-p-cresol (0.07 g, 0.33 mmol), and trans-di(ꢄ-
2.3.8. Synthesis of Compound 7
A DMAc solution (30 mL) of 6 (1.0 g, 1.66 mmol),
4-bromobenzaldehyde (0.34 g, 1.83 mmol), sodium
acetato)bis[o-(di-o-tolylphosphino)benzyl] dipalladium(II)
carbonate (0.53 g,De4li.v9e9redmmbyolP),ub2li,s6h-dini-gteTrte-cbhutnyol-lopg- y to: Chinese University of Hong Kong
(16 mg, 0.017 mmol) was stirred at 110 ꢁC for 16 h.
IP: 216.171.244.50 On: Wed, 14 Oct 2015 13:36:23
cresol (0.07 g, 0.33 mmol), and trans-di(ꢄ-acetato)bis[o-
Copyright: American Scientific Publishers
After removal of the solvent, the mixture was poured into
(di-o-tolylphosphino)benzyl] dipalladium(II) (16 mg,
0.017 mmol) was stirred at 110 ꢁC for 16 h. After removal
of the solvent, the mixture was poured into methylene
chloride and washed with water. The organic layer was
purified by column chromatography on a silica gel using
methylene chloride and n-hexane (1:5, v/v) as an elu-
ent. Yield (1.04 g, 89%). mp 300–302 ꢁC. 1H NMR
(400 MHz, DMSO-d6) ꢅ 7.10 (d, J = 16.5 Hz, 1 H,
–CH CH–), 7.30 (t, J = 7.7 Hz, 4 H, –Ph–carbazole),
7.44 (t, J = 7.7 Hz, 4 H, –Ph–carbazole), 7.49 (d, J =
8.8 Hz, 4 H, –N–Ph–carbazole), 7.50 (d, J = 16.5 Hz, 1 H,
–CH CH–), 7.53 (d, J = 8.8 Hz, 4 H, –N–Ph–carbazole),
methylene chloride and washed with water. After removal
of the organic solvent, the residue was purified by col-
umn chromatography on a silica gel using methylene chlo-
ride and n-hexane (1:5, v/v) as an eluent. Yield (550 mg,
ꢁ
1
43%). mp 254–257 C. H NMR (400 MHz, DMSO-d6)
ꢅ 3.90 (s, 3 H, –Ph–O–CH3), 3.98 (s, 3 H, –Ph–O–CH3),
7.20 (s, 1 H, CHO–Ph–CH ), 7.29 (t, J = 7.7 Hz, 4H,
–Ph–carbazole), 7.30 (d, J = 16.5 Hz, 1 H, –CH CH–),
7.35 (s, 1 H, CHO–Ph–CH ), 7.40 (d, J = 8.8 Hz, 2 H,
CH–Ph–N–), 7.43 (t, J = 7.7 Hz, 4 H, –Ph–carbazole),
7.45 (d, J = 16.5 Hz, 1 H, –CH CH–), 7.47 (d, J =
8.8 Hz, 4 H, –N–Ph–carbazole), 7.50 (d, J = 8.8 Hz,
4 H, –N–Ph–carbazole), 7.53 (d, J = 7.7 Hz, 4 H, –Ph–
carbazole), 7.59 (d, J = 8.8 Hz, 2 H, CH–Ph–N–), 8.16
(d, J = 7.7 Hz, 4 H, –Ph–carbazole), 10.4 (s, 1 H, –
Ph–CHO); 13C NMR (100.64 MHz, DMSO-d6) ꢅ 56.12,
56.24, 109.15, 109.72, 111.09, 115.14, 119.84, 120.18,
123.25, 124.29, 125.20, 125.83, 128.05, 128.18, 132.35,
132.61, 136.58, 140.85, 142.37, 146.15, 147.21, 187.91,
161.18, 156.94, 187.94.
7.57 (d, J = 8.8 Hz, 2 H,
7.7 Hz, 4 H, –Ph–carbazole), 7.80 (d, J = 7.3 Hz, 2 H,
CH–Ph–
CH–Ph–N–), 7.66 (d, J =
CH–Ph–CHO), 7.87 (d, J = 7.3 Hz, 2 H,
CHO), 7.99 (d, J = 8.8 Hz, 2 H, CH–Ph–N–), 8.16 (d,
J = 7.7 Hz, 4 H, –Ph–carbazole), 9.99 (s, 1 H, –Ph–CHO);
13C NMR (100.64 MHz, DMSO-d6) ꢅ 109.72, 119.87,
120.28, 123.26, 124.22, 125.29, 126.20, 126.67, 128.07,
128.13, 130.19, 131.34, 131.68, 132.71, 135.10, 140.84,
143.49, 146.10, 147.43, 191.37.
2.3.9. Synthesis of CB-2
2.3.11. Synthesis of CB-3
An acetonitrile solution (40 mL) of 7 (0.9 g, 1.28 mmol),
cyanoacetic acid (2.17 g, 25.50 mmol), and piperidine
(5.97 g, 70.13 mmol) was stirred at 90 C for 24 h. The
A piperidine (3.06 g, 0.36 mmol) was added into an ace-
tonitrile solution (40 mL) of 8 (0.5 g, 0.65 mmol) and
cyanoacetic acid (1.11 g, 13.10 mmol). The solution was
ꢁ
ꢁ
mixture solution was cooled at room temperature then
stirred at 90 C for 24 h. After removal of the solvent,
J. Nanosci. Nanotechnol. 15, 1434–1442, 2015
1437