448 Chem. Mater., Vol. 22, No. 2, 2010
Zhao et al.
to a similar procedure to 3a. It was purified by column chromato-
graphy (silica gel, hexane/DCM=3:1, v/v) to give pure 3b as a
white solid in 69% yield. 1H NMR (300 MHz, CDCl3, δ ppm):
7.37 (d, J=8.1 Hz, 1H, Ar-H), 7.29 (s, 1H, Ar-H), 6.87 (d, J=8.1
Hz, 1H, Ar-H), 4.05-3.99 (m, 4H, OCH2-), 1.86-1.77 (m, 4H,
OCH2-CH2-), 1.46-1.26 (br, 48H), 0.90-0.86 (br, 6H, -CH3).
13C NMR (75 MHz, CDCl3, δ ppm): 151.98, 148.54, 128.63,
119.54, 112.77, 83.51, 69.26, 68.88, 31.91, 29.68, 29.63, 29.60,
29.43, 29.41, 29.35, 29.20, 26.05, 25.99, 24.83, 22.67, 14.07. HR-EI
MS (m/z): found, 573.4803 ([MþHþ]); calcd for C36H65BO4,
572.4976.
analysis: calcd for C150H219N3O12: C 79.85, H 9.78, N 1.86, O
8.51; found: C 79.83, H 9.77, N 1.91.
Synthesis of 2,3,7,8,12,13-hexakis(3,4-bis(dodecyloxy)-
phenyl)-5,10,15-trihexyl-10,15-dihydro-5H-diindolo[3,2-a:30,20-c]-
carbazole (4b). Compound 4b was synthesized according to a
similar procedure to 4a. The crude product was purified by
column chromatography (silica gel, hexane/DCM=3/1, v/v) to
1
give the pure 4b in 74% yield. H NMR (500 MHz, CDCl3, δ
ppm): 8.32 (s, 3H), 7.63 (s, 3H), 6.94 (d, J=7.5 Hz, 6H), 6.86 (d,
J=7.5 Hz, 6H), 6.76-6.72 (m, 6H), 4.96 (br, 6H), 4.03-3.99 (m,
12H), 3.75-3.71 (m, 12H), 2.09 (br, 6H), 1.88-1.82 (m, 12H),
1.71-1.67 (m, 12H), 1.68-1.48 (m, 12H), 1.39-1.22 (br, 252H),
0.92-0.88 (m, 51H). 13C NMR (75 MHz, CDCl3, δ ppm):
148.44, 147.85, 147.64, 140.44, 139.53, 136.03, 135.74, 135.53,
132.97, 124.45, 123.96, 123.23, 122.50, 122.19, 116.86, 116.75,
113.49, 111.49, 103.12, 69.41, 69.21, 69.12, 47.27, 31.94, 31.45,
30.32, 30.20, 29.75, 29.69, 29.54, 29.51, 29.39, 29.23, 26.78,
26.16, 26.11, 22.69, 14.08. MALDI-TOF MS (m/z): found,
3518.62 ([MþHþ]); calcd for C240H399N3O12 (exact mass),
3516.07. Elemental analysis: calcd for C240H399N3O12: C
81.92, H 11.43, N 1.19, O 5.46; found: C 81.80, H 11.47 N 1.23.
Synthesis of TP-TATC6. A solution of 4a (225 mg, 0.1 mmol)
in dry DCM (80 mL) was degassed by bubbling through
nitrogen gas for 15 min. FeCl3 (228 mg, 1.4 mmol) in anhydrous
CH3NO2 (0.5 mL) was then added dropwise via a syringe over
the course of 15 min. The dark-green solution was kept stirring
and bubbling with a nitrogen flow for 30 min and then the
reaction was quenched with methanol (60 mL) The precipitate
was collected and washed with methanol before dissolved in
DCM (50 mL). The solution was washed with brine for twice
and dried over Na2SO4. The solvent was removed under vacuum
and the residue was purified by column chromatography (silica
gel, hexane/DCM=2/1, v/v) to give the title product TP-TATC6
as a yellow powder (156 mg, 69%): 1H NMR (500 MHz, CDCl3,
δ ppm): 9.43 (s, 3H), 8.67 (s, 3H), 8.35 (s, 3H), 8.27 (s, 3H), 7.96
(s, 3H), 7.95 (s, 3H), 5.38 (t, J=7.0 Hz, 6H), 4.38 (m, 12H), 4.30
(m, 12H), 2.08-1.97 (m, 30H), 1.71-1.61 (m, 30H), 1.48-1.42
(m, 48H), 1.23-1.11 (m, 12H), 1.04-0.94 (m, 36H), 0.60 (t, J=
7.5 Hz, 9H). 13C NMR (125 MHz, CDCl3, δ ppm): 149.62,
149.26, 149.21, 149.11, 141.73, 141.47, 125.92, 125.10, 124.38,
124.10, 123.78, 123.24, 115.68, 108.83, 108.58, 107.97, 107.74,
103.97, 103.25, 70.38, 70.12, 69.84, 69.78, 47.29, 31.77, 31.73,
31.27, 29.65, 29.53, 29.51, 29.11, 26.47, 25.99, 25.94, 25.92,
22.68, 22.31, 14.06, 13.72. MALDI-TOF MS (m/z): found,
2249.86 ([MþHþ]); calcd for C150H213N3O12 (exact mass),
2248.61. Elemental analysis: calcd for C150H213N3O12: C
80.06, H 9.54, N 1.87, O 8.53; found: C 80.10, H 9.52, N 1.90.
Synthesis of TP-TATC12. Compound TP-TATC12 was
synthesized by a similar procedure to compound TP-TATC6.
The crude product was purified by column chromatography
(silica gel, hexane/DCM=5:3, v/v) to give pure TP-TATC12 as a
Synthesis of 2,3,7,8,12,13-hexabromo-5,10,15-tridodecyl-10,
15-dihydro-5H-diindolo[3,2-a:30,20-c]carbazole (2b). A mix-
ture of 1 (2.47 g, 3.02 mmol) and KOH (2.52 g, 45 mmol) in
THF (50 mL) was heated to 70 °C and the 1-bromododecane
(2.48 g, 10.0 mmol) was added. The solution was kept reflux-
ing for 12 h under a nitrogen atmosphere, before it was cooled
to room temperature. The mixture was diluted with DCM
(150 mL) and washed with 10% HCl (2 ꢀ 100 mL) and then
brine. The organic layer was dried over Na2SO4, and the
solvents were removed under vacuum. The residue was puri-
fied by column chromatography (silica gel, hexane/DCM=
8:1, v/v) to give pure 2a as a pale white solid (2.94 g, 74%).
1H NMR (300 Hz, CDCl3, δ ppm): 8.21 (s, 3H), 7.69 (s, 3H),
4.37 (t, J=4.8 Hz, 6H), 1.86 (br, 6H), 1.29-1.20 (br, 54H),
0.88 (t, J=4.5 Hz, 9H). 13C NMR (75 MHz, CDCl3, δ ppm):
139.81, 138.40, 124.71, 122.52, 118.47, 115.17, 114.24,
100.97, 46.71, 31.94, 30.22, 29.68, 29.65, 29.61, 29.57, 29.52,
29.38, 29.30, 26.43, 22.71, 14.13. MALDI-TOF MS
(m/z): found, 1318.64 ([MþHþ]), 1239.47 ([M-BrþHþ]),
1159.28 ([M-2Br þ Hþ]), 1079.96 ([M-3BrþHþ]), 1001.25
([M-4BrþHþ]), 923.21 ([M-5BrþHþ]), 844.96 ([M-6Brþ
Hþ]); calcd for C60H81Br6N3 (exact mass), 1317.15.
Synthesis of 2,3,7,8,12,13-hexakis(3,4-bis(hexyloxy)phenyl)-
5,10,15-trihexyl-10,15-dihydro-5H- diindolo[3,2-a:30,20-c]carba-
zole (4a). A mixture of 3a (0.53 g, 0.5 mmol), 2a (1.58 g, 3.9
mmol), and Cs2CO3 (1.95 g, 6.0 mmol) in toluene (10 mL) in a
10-mL pressure vessel was carefully degassed by purging
through nitrogen before and after adding Pd(PPh3)4 (60 mg,
0.05 mmol). The vessel was then sealed and heated in the CEM
Discover system. The initial microwave power was set at 100 W,
and the reaction time was set as 30 min. The temperature was
monitored using a calibrated infrared temperature controller
mounted under the reaction vessel. The pressure was controlled
by a load cell connected to the vessel via the septum. After the set
temperature of 135 °C was reached, the microwave power
regulated itself to keep that temperature before cooling to room
temperature. The mixture was subsequently diluted with DCM
(50 mL) and then washed with 1 M aqueous HCl (30 mL) and
brine. The organic layer was dried over Na2SO4 and the solvent
was removed under vacuum. The residue was purified by
column chromatography (silica gel, hexane/DCM = 5/2, v/v)
to give the pure 4a in 82% yield. 1H NMR (300 MHz, CDCl3, δ
ppm): 8.31 (s, 3H), 7.61 (s, 3H), 6.93 (d, J=8.1 Hz, 6H), 6.86 (d,
J=8.1 Hz, 6H), 6.76-6.71 (m, 6H), 4.95 (br, 6H), 4.02-3.97 (m,
12H), 3.75-3.70 (m, 12H), 2.09 (br, 6H), 1.79-1.87 (m, 12H),
1.71-1.65 (m, 12H), 1.49-1.08 (br, 84H), 0.95-0.88 (m, 42H),
0.74 (t, J=6.9 Hz, 9H). 13C NMR (75 MHz, CDCl3, δ ppm):
148.42, 147.82, 147.61, 140.44, 139.51, 136.00, 135.74, 135.48,
132.96, 123.21, 122.47, 122.19, 116.79, 116.656, 113.43, 111.48,
103.09, 69.34, 69.17, 69.07, 47.27, 31.66, 31.64, 31.57, 30.30,
29.41, 29.38, 29.14, 26.48, 25.76, 25.70, 22.632, 22.49, 13.99,
13.91. MALDI-TOF MS (m/z): found, 2254.92 ([MþHþ]);
calcd for C150H219N3O12 (exact mass), 2254.66. Elemental
1
yellow powder in 72% yield. H NMR (500 MHz, CDCl3, δ
ppm): 9.44 (s, 3H), 8.67 (s, 3H), 8.35 (s, 3H), 8.27 (s, 3H), 7.95
(br, 6H), 5.39 (br, 6H), 4.42 (t, J=6.3 Hz, 6H), 4.38 (t, J=6.3 Hz,
6H), 4.31 (t, J=6.3 Hz, 12H), 2.06-1.99 (m, 30H), 1.69-1.62
(m, 30H), 1.56-1.47 (m, 30H), 1.47-1.03 (br, 174H), 0.92-0.82
(br, 72H), 0.77 (t, J=7.5, 9H), 13C NMR (125 MHz, CDCl3, δ
ppm): 149.57, 149.20, 149.15, 149.06, 141.73, 141.52, 125.93,
125.09, 124.38, 124.14, 123.76, 123.26, 115.69, 108.64, 108.46,
107.91, 107.69, 104.00, 103.29, 70.30, 70.09, 69.84, 69.77, 47.29,
31.95, 31.91, 31.81, 29.84, 29.79, 29.76, 29.74, 29.70, 29.61,
29.57, 29.51, 29.49, 29.42, 29.40, 29.38, 29.25, 29.17, 29.06,
26.77, 26.40, 26.36, 26.29, 22.70, 22.70, 22.66, 22.60, 14.12,
14.07, 14.04. MALDI-TOF MS (m/z): found, 3511.24