JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
measurement (PVM-154) monosilicon solar cell (NREL cali-
brated) to minimize spectral mismatch; a silicon photodiode
(Hamamatsu S1133) was used to check the uniformity of the
exposed area.
122.4, 141.2. MS (m/z): [M]þ calcd. for C18H20Br2N2, 424;
found, 424.
N,N0-Di(2-decyltetradecyl)perylene-3,4,9,10-
tetracarboxylic Diimide (6)
2,7-Dibromo-9-(6-bromohexyl)-9H-carbazole (2)
A mixture of perylene-3,4,9,10-tetracarboxylic acid anhydride
(1.50 g, 3.82 mmol), Zn(OAc)2 (0.84 g, 4.58 mmol), 2-decyl-
tetradecylamine (4.07 g, 11.5 mmol), and quinoline (20 mL)
was heated at 180 ꢀC overnight under N2. After cooling, the
mixture was poured into MeOH (200 mL), treated with 2 M
HCl (40 mL), and stirred overnight. The resulting precipitate
was filtered off, washed sequentially with water and MeOH,
and then dried under vacuum at 80 ꢀC to afford 6 (3.55 g,
87.3%) as a red solid.
1,6-Dibromohexane (2.94 mL, 19.1 mmol) was added to a
mixture of 2,7-dibromo-9H-carbazole (2.00 g, 6.15 mmol),
KOH (0.41 g,ꢀ7.31 mmol), and N,N-dimethylformamide (DMF,
40 mL) at 0 C. The system was stirred at room temperature
for 24 h and then diluted with water (200 mL). The solution
was extracted with EtOAc (3 ꢂ 50 mL), and the combined
organic layers dried (MgSO4) and concentrated under
reduced pressure. The crude product was purified through
column chromatography (EtOAc/hexane, 1:10) to afford 2
(2.25 g, 74.9%) as a white solid.
1H NMR (300 MHz, CDCl3): d 0.81–0.87 (m, 12H), 1.20–1.33
(m, 80H), 1.99 (br, 2H), 4.11 (d, J ¼ 6.9 Hz, 2H), 7.40 (d, J ¼
7.8 Hz, 4H), 8.53 (d, J ¼ 7.8 Hz, 4H). 13C NMR (75 MHz,
CDCl3): d 14.1, 22.7, 26.5, 29.3, 29.6, 29.7, 30.1, 31.7, 31.9,
31.9, 36.7, 44.7, 122.6, 123.0, 125.7, 128.9, 130.8, 133.7,
163.2. MS (m/z): [M]þ calcd. for C72H106N2O4, 1062.8; found,
1064.
1H NMR (300 MHz, CDCl3): d 1.27–1.53 (m, 4H), 1.79–1.92
(m, 4H), 3.39 (t, J ¼ 6.6 Hz, 2H), 4.21 (t, J ¼ 6.9 Hz, 2H),
7.34 (dd, J ¼ 8.4, 1.2 Hz, 2H), 7.52 (d, J ¼ 1.2 Hz, 2H), 7.89
(d, J ¼ 8.1 Hz, 2H). 13C NMR (75 MHz, CDCl3): d 26.3, 27.8,
28.6, 32.5, 33.6, 43.1, 111.9, 119.7, 121.3, 121.5, 122.6,
141.3. MS (m/z): [M]þ calcd. for C18H18Br3N, 486.9; found,
487.
N-(2-Decyltetradecyl)perylene-3,4,9,10-tetracarboxylic-
3,4-anhydride-9,10-imide (7)
2,7-Dibromo-9-(6-azidohexyl)-9H-carbazole (3)
Compound 2 (2.10 g, 4.30 mmol) and NaN3 (1.41 g, 21.7
mmol) were dissolved in DMF (30 mL) and heated at 85 C
A mixture of 6 (3.0 g, 2.82 mmol), KOH (0.43 g, 7.66 mmol),
and tert-butyl alcohol (80 mL) was stirred at 85 ꢀC for 40
min under N2. Upon cooling, acetic acid (10 mL) and 2 M
HCl (20 mL) were added. The red precipitate was filtered off
and washed sequentially with water, MeOH, and cold acetone
to afford 7 (1.34 g, 65.2%) as a red solid.
ꢀ
overnight. After cooling, the mixture was poured into water
(200 mL) and extracted with EtOAc (3 ꢂ 50 mL). The com-
bined organic layers were washed with brine, dried (MgSO4),
and concentrated under reduced pressure. The crude prod-
uct was purified through column chromatography (EtOAc/
hexane, 1:10) to afford 3 (1.75 g, 90.3%) as a viscous oil.
1H NMR (300 MHz, CDCl3): d 1.39–1.60 (m, 6H), 1.81–1.90
(m, 2H), 3.25 (t, J ¼ 6.9 Hz, 2H), 4.19 (t, J ¼ 7.2 Hz, 2H),
7.34 (dd, J ¼ 8.4, 1.2 Hz, 2H), 7.52 (d, J ¼ 1.2 Hz, 2H), 7.89
(d, J ¼ 8.1 Hz, 2H). 13C NMR (75 MHz, CDCl3): d 26.4, 26.7,
28.6, 28.7, 43.0, 51.2, 111.8, 119.7, 121.2, 121.4, 122.5,
141.2. MS (m/z): [M]þ calcd. for C18H18Br2N4, 450; found,
450.
1H NMR (300 MHz, CDCl3): 1H NMR (300 MHz, CDCl3): d
0.83–0.85 (m, 6H), 1.20–1.33 (m, 40H), 2.00 (m, 1H), 4.13
(m, 2H), 8.69 (br, 8H). MS (m/z): [M]þ calcd. for C48H57NO5,
727.4; found, 728.
N-(2-Decyltetradecyl)-N0-(2,7-dibromo-9-hexyl-9H-
carbazole)perylene-3,4,9,10-tetracarboxylic Diimide (M1)
A mixture of 4 (0.50 g, 1.18 mmol), 7 (0.78 g, 1.07 mmol),
Zn(OAc)2 (0.26 g, 1.42 mmol), and quinoline (15 mL) was
ꢀ
heated at 180 C for 4 h under N2. After cooling, the mixture
was poured into MeOH (100 mL), treated with 2 M HCl (20
mL), and stirred overnight. The resulting precipitate was col-
lected by vacuum filtration, washed sequentially with water
and MeOH, and then purified through column chromatogra-
phy (CHCl2) and recrystallization (EA/MeOH) to afford M1
(0.75 g, 62%) as a dark red solid.
2,7-Dibromo-9-(6-aminohexyl)-9H-carbazole (4)
A solution of 3 (1.5 g, 3.33 mmol) in Et2O (20 mL) was
added dropwise to a suspension of LiAlH4 (0.18 g, 4.75
mmol) in Et2O (20 mL) at 0 ꢀC and then the system was
stirred under N2 for 2 h. The mixture was diluted with Et2O
and then saturated aqueous Na2SO4 was slowly added. After
stirring for 1 h, the mixture was extracted with Et2O (3 ꢂ
50 mL). The combined organic layers were washed with
brine, dried (MgSO4), and concentrated under reduced pres-
sure. The crude product was purified through recrystalliza-
tion (EtOH/hexane) to afford 4 (1.21 g, 85.6%) as a yellow
solid.
1H NMR (300 MHz, CDCl3): d 0.78–0.87 (m, 6H), 1.14–1.47
(m, 44H), 1.75–1.82 (m, 4H), 1.98 (br, 1H), 4.07–4.15 (m,
6H), 7.21 (dd, J ¼ 8.1 Hz, 1.5 Hz, 2H), 7.43 (d, J ¼ 1.5 Hz,
2H), 7.73 (d, J ¼ 8.1 Hz, 2H), 8.22 (dd, J ¼ 8.4, 3.6 Hz, 4H),
8.41 (dd, J ¼ 8.1, 3.3 Hz, 4H). 13C NMR (75 MHz, CDCl3): d
14.1, 22.7, 26.5, 26.7, 26.8, 27.7, 28.6, 29.3, 29.6, 29.7, 30.1,
31.7, 31.9, 36.7, 40.3, 43.2, 44.7, 111.8, 119.6, 121.1, 121.3,
122.4, 122.6, 122.7, 122.9, 123.1, 125.8, 128.9, 128.9, 130.9,
133.8, 140.0, 141.1, 163.0, 163.4. MS (m/z): [M]þ calcd. for
1H NMR (300 MHz, CDCl3): d 1.36–1.48 (m, 6H), 1.79–1.88
(m, 2H), 2.38 (s, 2H), 2.72 (t, J ¼ 6.9 Hz, 2H), 4.17 (t, J ¼ 7.2
Hz, 2H), 7.33 (dd, J ¼ 8.4, 1.2 Hz, 2H), 7.51 (d, J ¼ 1.2 Hz,
2H), 7.87 (d, J ¼ 8.4 Hz, 2H). 13C NMR (75 MHz, CDCl3): d
26.5, 26.9, 28.6, 33.6, 42.0, 43.1, 111.8, 119.6, 121.2, 121.4,
C
C
66H75Br2N3O4, 1133.4; found, 1135. Anal. Calcd. for
66H75Br2N3O4: C, 69.90; H, 6.67; N, 3.71. Found: C, 69.66;
H, 6.62; N, 3.93.
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