(3C), 26.0 (3C), 22.7 (3C), 14.1 (3C). HRMS (FAB+) m/z
for C60H77IO3 972.4917, found 972.4905. Anal. Calcd for
C60H77IO3 (973.2): C 74.05, H 7.98; found: C 73.98, H 7.98.
1e: (n 5 12) yield 25%. 1H NMR (CDCl3, 300 MHz): d
8.01 (s, 1H), 7.62 (s, 1H), 7.52 (d, J 5 9.0 Hz, 2H), 7.490 (d,
J 5 9.0 Hz, 2H), 7.485 (d, J 5 8.4 Hz, 2H), 6.90–6.85 (m, 6H),
3.97 (m, 6H), 1.84–1.75 (m, 6H), 1.49–1.29 (m, 54H), 0.90 (m,
9H). 13C NMR (CDCl3, 75 MHz): d 159.7, 159.64, 159.58,
141.1, 134.1, 133.19, 133.15 (2C), 129.4, 126.2, 125.8, 114.8,
114.7, 114.6 (3C), 114.5, 99.0, 96.2, 95.2, 95.1, 90.0, 86.0, 85.8,
68.1 (3C), 31.9 (3C), 29.7 (6C), 29.6 (6C), 29.4 (3C), 29.3 (3C),
29.2 (3C), 26.0 (3C), 22.7 (3C), 14.1 (3C). HRMS (FAB+) m/z
for C66H89IO3 1056.5856, found 1056.5867. Anal. Calcd for
C66H89IO3 (1057.3): C 74.97, H 8.48; found: C 74.85, H 8.48.
1f: (n 5 14) yield 26%. 1H NMR (CDCl3, 300 MHz): d
8.01 (s, 1H), 7.62 (s, 1H), 7.52 (d, J 5 9.0 Hz, 2H), 7.481 (d,
J 5 9.0 Hz, 2H), 7.476 (d, J 5 9.0 Hz, 2H), 6.90–6.85 (m, 6H),
3.97 (m, 6H), 1.82–1.76 (m, 6H), 1.46–1.28 (m, 66H), 0.89 (m,
9H). 13C NMR (CDCl3, 75 MHz): d 159.8, 159.7, 159.6, 141.1,
134.1, 133.22, 133.17 (2C), 129.4, 126.2, 125.8, 114.8, 114.7,
114.6 (3C), 114.5, 99.0, 96.2, 95.2, 95.1, 90.0, 86.0, 85.8, 68.1
(3C), 31.9 (3C), 29.7 (9C), 29.62 (6C), 29.59 (3C), 29.40 (3C),
29.37 (3C), 29.2 (3C), 26.0 (3C), 22.7 (3C), 14.1 (3C). HRMS
(FAB+) m/z for C72H101IO3 1140.6795, found 1140.6754. Anal.
Calcd for C72H101IO3 (1441.5): C 75.76, H 8.92; found: C
75.89, H 8.97.
1g: (n 5 16) yield 14%. 1H NMR (CDCl3, 300 MHz): d
8.01 (s, 1H), 7.62 (s, 1H), 7.52 (d, J 5 9.0 Hz, 2H), 7.48 (d,
J 5 8.4 Hz, 2H), 7.47 (d, J 5 9.3 Hz, 2H), 6.90–6.85 (m, 6H),
3.97 (m, 6H), 1.82–1.77 (m, 6H), 1.46–1.27 (m, 78H), 0.88 (m,
9H). 13C NMR (CDCl3, 75 MHz): d 159.8, 159.7, 159.6, 141.1,
134.1, 133.21, 133.17 (2C), 129.4, 126.2, 125.8, 114.8, 114.7,
114.6 (3C), 114.5, 99.0, 96.2, 95.2, 95.1, 90.0, 86.0, 85.8, 68.2
(3C), 31.9 (3C), 29.7 (18C), 29.6 (9C), 29.4 (3C), 29.2 (3C), 26.0
(3C), 22.7 (3C), 14.1 (3C). HRMS (FAB+) m/z for C78H113IO3
1224.7734, found 1224.7751. Anal. Calcd for C78H113IO3
(1225.6): C 76.44, H 9.29; found: C 76.52, H 9.29.
840.4110; for C54H6581BrO3 842.4097, found 842.4080. Anal.
Calcd for C54H65BrO3 (842.0): C 77.03, H 7.78; found: C
76.82, H 7.83.
1-Chloro-2,4,5-tris(4-octyloxyphenylethynyl)benzene (3). To
a
mixture of trans-dichlorobis(triphenylphosphine)palla-
dium(II) (73 mg, 0.10 mmol), copper iodide (25 mg,
0.13 mmol), and 1-chloro-2,4,5-triiodothiophene (502 mg,
1.02 mmol) in triethylamine (30 mL) was added 1-ethynyl-4-
octyloxybenzene (820 mg, 3.56 mmol) dropwise at room
temperature. The solution was allowed to stir at room
temperature for 24 h and then dichloromethane (100 mL)
was added. The reaction mixture was washed with NH4Cl(aq)
(100 mL 6 3), H2O (100 mL 6 3), and dried over MgSO4.
After removal of the solvent, the residue was purified by
column chromatography (SiO2, n-hexane–dichloromethane
5 : 1) to yield 3 as a white solid (760 mg, 0.95 mmol, 93%).
1H NMR (CDCl3, 300 MHz): d 7.68 (s, 1H), 7.56 (s, 1H), 7.51–
7.47 (m, 6H), 6.90–6.85 (m, 6H), 3.97 (t, J 5 6.7 Hz, 6H), 1.84–
1.75 (m, 6H), 1.49–1.30 (m, 30H), 0.90 (m, 9H). 13C NMR
(CDCl3, 75 MHz): d 159.8, 159.75, 159.70, 135.4, 134.4, 133.25
(2C), 133.23 (2C), 133.1 (2C), 131.7, 126.2, 124.5, 123.0, 114.8,
114.6 (7C), 114.5, 96.6, 96.2, 94.7, 86.2, 85.7, 84.5, 68.1 (3C),
31.8 (3C), 29.3 (3C), 29.2 (6C), 26.0 (3C), 22.6 (3C), 14.1 (3C).
HRMS (EI+) m/z for C54H6535ClO3 796.4622, found 796.4605;
for C54H6537ClO3 798.4593, found 798.4581. Anal. Calcd for
C54H65ClO3 (797.5): C 81.32, H 8.21; found: C 81.23, H 8.26.
1,2,4-Tris(4-octyloxyphenylethynyl)benzene (4). To a solu-
tion of 1c (308 mg, 0.35 mmol) in THF (30 mL) at 270 uC was
added 1.6 M n-BuLi (0.68 mmol) dropwise under a nitrogen
atmosphere. When the addition was completed, the reaction
mixture was stirred at 270 uC for further 30 min. The reaction
mixture was allowed to stir at room temperature for 24 h and
then to the reaction mixture was added dichloromethane
(50 mL). The reaction mixture was washed with H2O
(100 mL 6 3) and dried over MgSO4. After removal of the
solvent, the residue was purified by column chromatography
(SiO2, n-hexane–dichloromethane 5 : 1) to yield 4 as a white
solid (216 mg, 0.28 mmol, 84%). 1H NMR (CDCl3, 300 MHz):
d 7.68 (d, J 5 1.5 Hz, 1H), 7.51–7.39 (m, 8H), 6.88–6.86 (m,
6H), 3.97 (m, 6H), 1.82–1.77 (m, 6H), 1.46–1.30 (m, 30H), 0.90
(m, 9H). 13C NMR (CDCl3, 75 MHz): d 159.5 (3C), 134.3,
133.1 (6C), 131.4, 130.3, 126.2, 125.3, 123.1, 115.1, 114.8, 114.6
(7C), 95.3, 94.1, 91.6, 87.3, 87.2, 86.6, 68.1 (3C), 31.8 (3C), 29.3
(3C), 29.2 (6C), 26.0 (3C), 22.6 (3C), 14.1 (3C). HRMS (EI+)
m/z for C54H66O3 762.5012, found 762.5009. Anal. Calcd for
C54H66O3 (763.1): C 84.99, H 8.72; found: C 84.86, H 8.74.
1-Bromo-2,4,5-tris(4-octyloxyphenylethynyl)benzene (2). To
a
mixture of trans-dichlorobis(triphenylphosphine)palla-
dium(II) (260 mg, 0.37 mmol), copper iodide (142 mg,
0.75 mmol), and 1-bromo-2,4,5-triiodothiophene (2.00 g,
3.74 mmol) in triethylamine (50 mL) was added 1-ethynyl-4-
octyloxybenzene (3.02 g, 13.09 mmol) dropwise at room
temperature. The solution was allowed to stir at room
temperature for 24 h and then dichloromethane (100 mL)
was added. The reaction mixture was washed with NH4Cl(aq)
(100 mL 6 3), H2O (100 mL 6 3), and dried over MgSO4.
After removal of the solvent, the residue was purified by
column chromatography (SiO2, n-hexane–dichloromethane
5 : 1) to yield 2 as a pale yellow solid (2.02 mg, 2.39 mmol,
64%). 1H NMR (CDCl3, 300 MHz): d 7.75 (s, 1H), 7.67 (s,
1H), 7.51–7.46 (m, 6H), 6.90–6.85 (m, 6H), 3.98 (t, J 5 6.5 Hz,
6H), 1.84–1.75 (m, 6H), 1.49–1.26 (m, 30H), 0.89 (t, J 5 6.9 Hz,
9H). 13C NMR (CDCl3, 75 MHz): d 159.8, 159.7, 159.6, 135.2,
134.9, 133.24 (4C), 133.15 (2C), 126.3, 125.1, 125.0, 123.9,
114.8, 114.6 (7C), 114.5, 96.3, 96.0, 94.9, 86.4, 86.0, 85.8, 68.1
(3C), 31.8 (3C), 29.3 (6C), 29.2 (3C), 26.0 (3C), 22.6 (3C), 14.1
(3C). HRMS (FAB+) m/z for C54H6579BrO3 840.4117, found
1,3-Bis-(4-octyloxyphenylethynyl)benzene (5). To a mixture
of trans-dichlorobis(triphenylphosphine)palladium(II) (31 mg,
0.05 mmol), copper iodide (10 mg, 0.05 mmol), and 1,3-
diiodobenzene (300 mg, 0.91 mmol) in triethylamine (40 mL)
was added 1-ethynyl-4-octyloxybenzene (520 mg, 2.26 mmol)
dropwise at room temperature. The reaction mixture was
allowed to stir stirred at room temperature for 3 h and then to
the reaction mixture was added dichloromethane (100 mL).
The reaction mixture was washed with NH4Cl(aq) (100 mL 6
3), H2O (100 mL 6 3), and dried over MgSO4. After removal
This journal is ß The Royal Society of Chemistry 2005
J. Mater. Chem., 2005, 15, 4854–4861 | 4859