filtration, dried and purified by column chromatography over silica gel
eluting with a mixture of dichloromethane:n-hexane (1:2) followed by
Synthesis
of
9′,9′′-(9,9′-spirobi[fluorene]-2,7-diyl)bis-9′H-9,3′:6′,9′′-
tercarbazole (SBFC-G2): Copper(I) iodide (0.014 g, 0.075 mmol),
18-crown-6 (0.0065 g, 0.0025 mmol), potassium carbonate (0.412 g,
3 mmol), carbazole (0.5 g, 3 mmol), and DMAc (4 mL) were added
to a round-bottom flask and vigorously stirred at 165 °C under argon.
After stirring and refluxing for 2 h, 5 (0.72 g, 0.75 mmol) as a solution in
hot DMAc (4 mL) was added into the mixture slowly. The final reaction
medium was heated to reflux for 24 h. The reaction solution was poured
into water (150 mL), the precipitate was collected by filtration, dried and
purified by column chromatography over silica gel eluting with a mixture
of dichloromethane:n-hexane (1:2) followed by recrystallization from a
mixture of dichloromethane-methanol gave a white solid (0.78 g, 80%).
1H NMR (400 MHz, CDCl3, 25°C, TMS): δ (ppm) = 8.27–8.25 (d, 2H),
8.20–8.16 (t, 11H), 7.85–7.80 (dd, 4H), 7.55–7.49 (dd, 8H), 7.41–7.33
(m, 18H), 7.31–7.25 (m, 11H), 7.20 (d, 2H), 7.10–7.08 (d, 2H); IR (ATR):
ν = 3045, 2657, 2355, 2328, 2113, 1913, 1594, 1467, 1448, 1309, 1276,
1223, 1153, 809, 741, 720 cm−1 ; MALDI-TOF (m/z): [M+] calcd. for
C97H58N6, 1307.5389; found 1307.4600.
recrystallization from
a mixture of dichloromethane-methanol gave
white solid (0.82 g, 80%). 1H NMR (400 MHz, CDCl3, 25°C, TMS): δ
(ppm) = 8.33 (d, 4H), 8.18–8.16 (d, 10H), 7.81–7.79 (m, 4H), 7.74–7.71
(m, 4H), 7.68–7.65 (dd, 4H), 7.42–7.41 (t, 4H), 7.31–7.28 (m, 8H),
2.23–2.19 (m, 4H), 1.19–1.14 (m, 21H), 1.00–0.97 (m, 4H), 0.73–
0.69 (m, 5H); 13C NMR (100 MHz, CDCl3, 25°C, TMS): δ (ppm) =
142.0, 141.0, 130.7, 126.6, 126.1, 124.3, 123.4, 120.6, 120.0, 109.9, 32.02,
29.6, 29.4, 22.8, 14.2; IR (ATR): ν = 3045, 2916, 2846, 2663, 2318, 2102,
1588, 1465, 1448, 1333, 1314, 1276, 1225, 1016, 801, 741, 717, 634 cm−1 ;
MALDI-TOF (m/z): [M+] calcd. for C101H84N6, 1381.7881; found 1381.6800.
Synthesis of 9,9′-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(3,6-di-2-thienyl-
9H-carbazole) (OFCT-G2): A mixture of
1 (0.77 g, 0.75 mmol),
2-thiopheneboronic acid (0.38 g, 3 mmol), Pd(PPh3)4 (0.02 g, 0.02 mmol),
aqueous solution of 2 M Na2CO3 (12.5 mL, 25.00 mmol) and THF
(20 mL) was degassed with Ar for 5 minute. The reaction mixture was
stirred at reflux under Ar for 24 h. After being cooled to room temperature,
distilled water (100 mL) was added. The mixture was extracted with
dichloromethane (2 × 50 mL), washed with water (100 mL) and brine (100
mL), dried over anhydrous Na2SO4, filtered and the solvents were removed
under vacuum. Purification by column chromatography over silica gel
eluting with a mixture of dichloromethane:n-hexane (1:2) afforded pale
green solids (0.67 g, 85%). 1H NMR (400 MHz, CDCl3, 25°C, TMS): δ
(ppm) = 8.44 (d, 4H), 8.03–8.01 (d, 2H), 7.75–7.72 (dd, 4H), 7.64–7.61
(d, 4H), 7.48–7.46 (d, 4H), 7.41–7.40 (dd, 4H), 7.31–7.30 (dd, 4H), 7.16–
7.13 (m, 4H), 2.08–2.06 (m, 3H), 1.20 (broad s, 27H), 0.85–0.82 (t, 4H);
13C NMR (100 MHz, CDCl3, 25°C, TMS): δ (ppm) = 145.5, 141.1, 139.9,
128.2, 127.4, 125.2, 124.2, 124.1, 122.6, 110.5, 56.0, 32.1, 30.2, 29.8, 29.6,
29.5, 22.8, 14.3; IR (ATR): ν = 2916, 2846, 2657, 2345, 2102, 1913, 1604,
1580, 1475, 1427, 1357, 1284, 1225, 870, 801, 685 cm−1 ; MALDI-TOF
(m/z): [M+]: calcd. for C69H64N2S4, 1049.5239; found 1048.3900.
Synthesis of 9,9′-(9,9′-spirobi[fluorene]-2,7-diyl)bis-9H-carbazole (SBFC-
G1): Copper(I) iodide (0.028 g, 0.15 mmol), 18-crown-6 (0.013 g,
0.05 mmol), potassium carbonate (0.825 g, 6 mmol), carbazole (1 g,
6 mmol), and DMAc (7.5 mL) were added to a round-bottom flask and
vigorously stirred at 165 °C under argon. After stirring and refluxing for
2 h, 2,7-dibromo-9,9′-spirobifluorene (1.42 g, 3 mmol) as a solution in
hot DMAc (7.5 mL) was added into the mixture slowly. The final reaction
medium was heated to reflux for 24 h. Then the reaction solution was
poured into water (300 mL), the precipitate was collected by filtration,
dried and purified by column chromatography over silica gel eluting with
a mixture of dichloromethane:n-hexane (1:4) followed by recrystallization
from a mixture of dichloromethane-methanol gave a white solid (1.64 g,
85%). 1H NMR (400 MHz, CDCl3, 25°C, TMS): δ (ppm) = 8.13–8.12
(d, 2H), 8.08–8.06 (d, 4H), 7.77–7.75 (d, 2H), 7.67–7.64 (dd, 2H),
7.39–7.37 (d, 2H), 7.35–7.34 (dd, 1H), 7.32–7.30 (d, 4H), 7.25–7.20 (m,
11H), 7.01–7.00 (d, 2H); 13C NMR (100 MHz, CDCl3, 25°C, TMS): δ
(ppm) = 151.4, 147.8, 142.0, 140.8, 140.2, 137.6, 128.4, 126.8, 126.0,
123.9, 123.5, 123.0, 121.4, 120.5, 120.4, 120.1, 119.6, 110.7, 109.8. IR
(ATR): ν = 3045, 2657, 2355, 2118, 1594, 1470, 1443, 1330, 1311, 1228,
1153, 819, 741, 717 cm−1 ; MALDI-TOF (m/z): [M+] calcd. for C49H30N2,
646.776; found 646.1400.
Synthesis
9H-carbazole) (SBFCT-G2): A mixture of 5 (0.72 g, 0.75 mmol),
2-thiopheneboronic acid (0.38 g, mmol), Pd(PPh3)4 (0.02 g,
of
9,9′-(9,9′-spirobi[fluorene]-2,7-diyl)bis(3,6-di-2-thienyl-
3
0.02 mmol), aqueous solution of 2 M Na2CO3 (12.5 mL, 25.00 mmol)
and THF (20 mL) was degassed with argon for 5 minute. The reaction
mixture was stirred at reflux under Ar for 24 h. After being cooled to
room temperature water (100 mL) was added. The mixture was extracted
with dichloromethane (2 × 50 mL), washed with water (100 mL) and
brine (100 mL), dried over anhydrous Na2SO4, filtered and the solvents
were removed under vacuum. Purification by column chromatography
over silica gel eluting with a mixture of dichloromethane:n-hexane (1:2)
afforded pale green solids (0.62 g, 85%). 1H NMR (400 MHz, CDCl3,
25°C, TMS): δ (ppm) = 8.28 (s, 4H), 8.14–8.12 (d, 2H), 7.80–7.78 (d,
2H), 7.64–7.62 (dd, 2H), 7.57–7.55 (dd, 4H), 7.41–7.37 (t, 2H), 7.32–7.31
(d, 4H), 7.26–7.18 (m, 8H), 7.10–7.08 (t, 4H), 7.01–6.99 (d, 4H); 13C
NMR (100 MHz, CDCl3, 25°C, TMS): δ (ppm) = 140.7, 128.2, 127.3, 124.1,
123.9, 122.5, 110.3; IR (ATR): ν = 3056, 2921, 2846, 2657, 2328, 2102,
1602, 1475, 1424, 1357, 1287, 1225, 801, 731, 682 cm−1 ; MALDI-TOF
(m/z): [M+] calcd. for C65H38N2S4, 975.2747; found 974.1600.
Synthesis of 9,9′-spiro[cyclododecane-1,9′-fluorene]-2′,7′-diylbis(3,6-
dibromo-9H-carbazole) (10): NBS (1.05 g, 6 mmol) was added in small
portions to a solution of SFC-G1 (0.97 g, 1.5 mmol) in THF (40 mL).
The reaction mixture was stirred at room temperature under argon
atmosphere for 18 h. THF was removed to dryness and dichloromethane
(100 mL) was added to the remaning solid. The organic phase was
washed with water (2 × 100 mL), brine (100 mL), dried over anhydrous
Na2SO4, filtered and the solvents were removed to dryness. Purification
by recrystallization from a mixture of dichloromethane and methanol
gave a white solid (1.30 g, 90%). IR (ATR): ν = 3040, 2927, 2857, 2657,
2323, 2118, 1709, 1588, 1465, 1430, 1354, 1314, 1271, 1223, 1053, 1016,
790, 731, 631 cm−1
.
Synthesis of 9′,9′′-spiro[cyclododecane-1,9′-fluorene]-2′,7′-diylbis-9′H-
9,3′:6′,9′′-tercarbazole (SFC-G2): Copper(I) iodide (0.009 g, 0.05 mmol),
18-crown-6 (0.004 g, 0.016 mmol), potassium carbonate (0.27 g,
2 mmol), carbazole (1 g, 2 mmol), and DMAc (2.5 mL) were added to a
round-bottom flask and vigorously stirred at 165 °C under argon. After
stirring and refluxing for 2 h, 10 (0.48 g, 0.5 mmol) as a solution in hot
DMAc (2.5 mL) was added into the mixture slowly. The final reaction
medium was refluxed for 24 h. After being cooled to room temperature,
the reaction solution was poured into water (100 mL), the precipitate
was collected by filtration, dried and purified by column chromatography
over silica gel eluting with a mixture of dichloromethane:n-hexane
(1:2) followed by recrystallization from a mixture of dichloromethane-
Synthesis of 9,9′-(9,9′-spirobi[fluorene]-2,7-diyl)bis(3,6-dibromo-9H-
carbazole) (5) NBS (1.41 g, 8 mmol) was added in small portions to
a solution of SBFC-G1 (1.29 g, 2 mmol) in THF (50 mL). The reaction
mixture was stirred at room temperature under argon atmosphere for
18 h. THF were removed to dryness than dichloromethane (100 mL)
was added to the resulting solid. The organic phase was washed with
water (2 × 100 mL), brine (100 mL), dried over anhydrous Na2SO4,
filtered and the solvents were removed under vacuum. Purification by
recrystallization from a mixture of dichloromethane-methanol gave a
white solid (1.73 g, 90%). 1H NMR (400 MHz, CDCl3, 25°C, TMS): δ
(ppm) = 8.07–8.06 (d, 2 H), 8.01(s, 1H), 7.99 (s, 1H), 7.82–7.76
(m, 4H), 7.57–7.54 (dd, 2H), 7.49–7.47 (dd, 2H), 7.40–7.34 (m, 6H),
7.19–7.15 (t, 2H), 7.01–6.98 (d, 2H), 6.93–6.92 (d, 1H), 6.84–6.80 (t,
3H); IR (ATR): ν = 3045, 2657, 2318, 2113, 1602, 1465, 1430, 1276, 1228,
1
methanol gave a white solid (0.52 g, 80%). H NMR (400 MHz, CDCl3,
25°C, TMS): δ (ppm) = 8.35 (s, 4H), 8.19–8.16 (t, 10H), 7.93 (s, 2H),
7.82–7.80 (d, 2H), 7.75–7.67 (dd, 8H), 7.44–7.41 (t, 16H), 7.32–7.29 (t,
8H), 2.00–1.94 (d, 7H), 1.50 (broad s, 15H); 13C NMR (100 MHz, CDCl3,
25°C, TMS): δ (ppm) = 142.0, 141.2, 130.7, 126.1, 124.2, 123.4, 120.5,
119.9, 119.6, 109.9; IR (ATR): ν = 3051, 2927, 2851, 2668, 2318, 2086,
1594, 1569, 1470, 1448, 1333, 1311, 1276, 1225, 1155, 1010, 919, 814,
1053, 1016, 860, 803, 725, 631 cm−1
.
©
4160 wileyonlinelibrary.com
2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Funct. Mater. 2010, 20, 4152–4161