9114 Inorganic Chemistry, Vol. 48, No. 19, 2009
Hayek et al.
give the desired product 5 as a white powder (202 mg, 90%). 1H
NMR (400 MHz, CDCl3, 25 °C): δ 7.71 (s, 4H), 3,12 (s, 2H),
1.19 (qt, 8H, J1 =7.2 Hz, J2 = 7.2 Hz), 0.81-0.75 (m, 20H),
0.68-0.63 (m, 8H). 13C NMR (100 MHz, CDCl3, 25 °C): δ
136.64; 102.76; 79.47; 73.74; 27.25; 25.97; 13.95. 11B-NMR (128
MHz, CDCl3, 25 °C): δ 2.5 ppm. MS: m/z 375.2 (calcd for
C22H33B2N4/M- Bu m/z 375.3).
12H, J = 7.23 Hz). 13C NMR (100 MHz, CDCl3, 25 °C): δ
147.48; 147.40; 140.68; 139.94; 136.66; 136.52; 131.44; 131.34;
130.19; 130.17; 129.24; 128.74; 128.19; 128.05; 127.32; 127.28;
126.84; 126.67; 126.67; 126.46; 126.37; 125.84; 124.47; 123.52;
123.02; 122.76; 77.16; 29.79; 29.65; 27.53; 26.32; 26.11; 14.03.
HRMS: m/z 1075.6725 (calcd for C74H81B2N6 m/z 1075.6725).
IR (KBr pellet) ν cm-1: 3129 (C-H); 1653, 1590 1369 (pz).
Mp=222 °C.
Chromophore 10. Under an argon atmosphere, 270 mg of 2,6-
diethynyl-4,4,8,8-tetrabutylpyrazabole 5 (0.62 mmol) were dis-
solved in anhydrous THF (30 mL). Bis(triphenylphosphine)-
palladium(II) chloride (43.8 mg, 0.06 mmol), CuI (11.8 mg,
0.06 mmol) and 6 (10 g, 28 mmol) in diethylamine (10 mL) were
added. The mixture was heated at 60 °C for 24 h. The solvents
were evaporated under vacuum, and the residue is dissolved in
diethyl ether and washed with water. The crude product was
purified by column chromatography (silica, cyclohexane) to
give 10 as yellow oil (587 mg, 50%). 1H NMR (400 MHz,
CDCl3, 25 °C): δ 7.79 (s, 4H), 7.51 (s, 8H), 7.09-6.94 (AB,
4H, J=16.00 Hz), 6.74 (s, 4H), 4.06-3.98 (m, 12H), 1.87-1.76
(m, 12H), 1.51-1.45 (m, 8H), 1.30-1.19 (m, 124H), 0.91 (t, 18H,
J=6.58 Hz), 0.82 (t, 12H, J=7.23 Hz). 13C NMR (100 MHz,
CDCl3, 25 °C): δ 153.31; 138.64; 137.59; 137.59; 137.55; 137.23;
136.04; 135.96; 132.18; 131.66; 130.00; 126.79; 126.31; 121.51;
105.37; 104.16; 104.07; 91.34; 80.03; 73.51; 69.18; 31.93; 31.92;
31.34; 29.74; 29.72; 29.70; 29.68; 29.66; 29.60; 29.44; 29.41;
29.38; 29.36; 27.39; 27.33; 26.11; 26.08; 26.02; 25.96; 22.68;
14.09; 14.03. HRMS: m/z 1894.6227 (calcd for C126H207B2N4O6
m/z 1894.6229). Mp > 250 °C.
(Z)-4-Iodo-30,40,50-tridodecyloxystilbene (6). Diethyl 4-iodo-
benzylphosphonate1 (1 g, 2.80 mmol) was dissolved in dry THF
(10 mL), then NaH (60% in oil, 565 mg, 14 mmol) was added.
After the effervescence ceased, the suspension was stirred for 1 h
at 50 °C under an argon atmosphere. Then a solution of 3,4,5-
tridodecyloxybenzaldehyde (1.85 g, 2.80 mmol) in anhydrous
THF (40 mL) was added. The mixture was stirred under reflux
for 2 h. After cooling, the solid is filtered off and the filtrate was
quenched by EtOH. Solvents are evaporated under vacuum, and
the solid residue was dissolved in CH2Cl2 and washed with water
(10 mL). The organic phase was dried over MgSO4 and the
solvent evaporated. The resulting solid product was recrystal-
1
lized in methanol to give 6 as a white solid (2.04 g, 85%). H
NMR (400 MHz, CDCl3, 25 °C): δ 7.66 (d, 2H, J=8.33 Hz), 7.23
(d, 2H, J=8.55 Hz), 7.03-6.85 (AB, 2H, J=16.23 Hz), 6.70 (s,
2H), 4.04-3.95 (m, 6H), 1.87-1.71 (m, 6H), 1.50-1.48 (m, 6H),
1.36-1.27 (m, 48H), 0.89 (t, 9H, J=6.36 Hz). 13C NMR (100
MHz, CDCl3, 25 °C): δ 153.29; 138.55; 137.66; 136.90; 132.04;
129.69; 128.02; 126.42; 105.26; 92.41; 73.49; 69.15; 31.91; 31.89;
30.30; 29.72; 29.70; 29.68; 29.66; 29.62; 29.58; 29.39; 29.36;
29.33; 26.08; 22.66; 14.08. HRMS: m/z 859.5453 (calcd for
C50H84IO3 m/z 859.5460).
Chromophore 11. Under an argon atmosphere, 200 mg of 2,6-
diethynyl-4,4,8,8-tetrabutylpyrazabole 5 (0.46 mmol) were
dissolved in anhydrous THF (30 mL). Bis(triphenylphosphine)-
palladium(II) chloride (34 mg, 0.046 mmol), CuI (10 mg,
0.046 mmol), and 7 (438 mg, 0.92 mmol) in diethylamine
(10 mL) were added. The mixture was heated at 60 °C for 48
h. The solvents were evaporated under vacuum, and the residue
was dissolved in diethyl ether and washed with water. The crude
product was purified by column chromatography (silica, cyclo-
hexane/MeOH 98/2 in vol.) to give 11 as a yellow solid (258 mg,
50%). 1H NMR (400 MHz, CDCl3, 25 °C): δ 7.77 (s, 4H),
7.49 (s, 8H), 7.40 (d, 2H, J = 8.99 Hz), 7.30-7.24 (m, 8H),
7.14-6.95 (m, 20H), 1.26-1.15 (m, 8H), 0.86-0.71 (m,
16H), 0.80 (t, 12H, J=7.24 Hz). 13C NMR (100 MHz, CDCl3,
25 °C): δ 147.40; 137.76; 137.23; 135.95; 131.64; 129.27; 127.44;
126.21; 126.03; 124.58; 123.28; 123.13104.02; 102.55;
91.35.79.93; 30.13; 29.66; 27.36; 27.30; 26.85; 26.08; 26.01.
HRMS: m/z 1123.6701 (calcd for C78H80B2N6 m/z 1123.6708).
Mp > 250 °C.
Chromophore 13. Under an argon atmosphere, 12 (170 mg,
0.49 mmol), 4,4,8,8-tetrabutyl-2,6-diiodopyrazabole 2 (170 mg,
0.27 mmol), Pd(PPh3)2Cl2 (10 mg, 0.015 mmol) were suspended
in a mixture of THF (30 mL) and i-Pr2NH (5 mL). Then CuI (4.7
mg, 0.024 mmol) was added. This mixture was sonicated 30 min
and stirred for 2 days at room temperature. The solvents were
removed under vacuum, and the crude product was purified by
column chromatography (silica, cyclohexane-MeOH 95-5 in
vol.) to give 13 as a reddish solid (131 mg, 50%). 1H NMR (400
MHz, CDCl3, 25 °C): δ 7.80 (s, 4H), 7.67 (d, 4H, J = 8.11 Hz),
7.31 (d, 4H, J=7.90 Hz), 6.00 (s, 4H), 2.57 (s, 12H), 1.43 (s,
12H), 1.22-1.15 (m, 8H), 0.89-0.69 (m, 16H), 0.80 (t, 12H, J=
7.23 Hz). 13C NMR (100 MHz, CDCl3, 25 °C): δ 155.79; 142.89;
140.58; 136.12; 135.16; 132.04; 128.41; 128.30; 123.62; 121.35;
103.61; 90.49; 80.68; 77.16; 31.39; 30.14; 29.65; 27.36; 26.04;
22.64; 14.56; 14.50; 14.01. 11B-NMR (128 MHz, CDCl3, 25 °C):
δ 0.8 (t, J=32 Hz) ppm. 19F-NMR (376 MHz, CDCl3, 25 °C): δ
-146 (q, J = 32 Hz) ppm. HRMS: m/z 1077.6574 (calcd for
C64H77B4F4N8 m/z 1077.6579). Mp > 250 °C.
Chromophore 8. In a three necked flask under an argon
atmosphere, 3 (430 mg, 0.62 mmol) Pd(OAc)2 (50 mg, 0.22 mmol)
and tri-o-tolylphosphine (TOP) (144 mg, 0.47 mmol) were
deaerated. Triethylamine (30 mL) and xylenes (60 mL) were
then added. The mixture was warmed up to 60 °C for 1.5 h.
A solution of 3,4,5-tridodecyloxystyrene13 (895 mg, 1.36 mmol)
in xylenes (10 mL) was added slowly, and the temperature was
raised to 120 °C. This mixture was stirred at 120 °C for a week.
The solvents were removed under vacuum, and then the crude
product was dissolved in methylene chloride and washed with
water. After evaporation of the solvents, the product was
purified by column chromatography (silica, cyclohexane) to
1
give 8 in 20% yield as a yellow oil (228 mg). H NMR (400
MHz, CDCl3, 25 °C): δ 7.86 (s, 4H), 7.56 (s, 8H), 7.08-6.96 (AB,
4H, J=16.01 Hz), 6.74 (s, 4H), 4.04 (t, 8H, J=6.57 Hz), 3.98 (t,
4H, J = 6.58 Hz), 1.89-1.60 (m, 12H), 1.50-1.45 (m, 8H),
1.40-1.15 (m, 124H), 0.89 (t, 18H, J=6.58 Hz), 0.79 (t, 12H,
J=7.24 Hz). 13C NMR (100 MHz, CDCl3, 25 °C): δ 153.30;
138.39; 136.30; 132.37; 130.31; 130.20; 128.79; 127.04; 126.91;
125.84; 122.74; 105.20; 73.50; 69.17; 43.42; 31.90; 31.89; 30.31;
30.13; 29.72; 29.72; 29.70; 29.67; 29.66; 29.63; 29.61; 29.58;
29.42; 29.39; 29.36; 29.33; 27.53; 26.87; 26.85; 26.09; 22.65;
14.07; 14.03. HRMS: m/z 1884.5805 (calcd for C122H206B2N4-
O6 þ K m/z 1884.5755). IR (KBr pellet) ν cm-1: 3029 (C-H);
1663, 1568 1369 (pz). Mp=198 °C.
Chromophore 9. In a three necked flask under an argon atmo-
sphere, 3 (250 mg, 0.62 mmol), Pd(OAc)2 (32 mg, 0.14 mmol),
and TOP (82 mg, 0.27 mmol) were deaerated. Triethylamine
(40 mL) and xylenes (60 mL) were then added. The mixture was
warmed up to 60 °C for 1.5 h. A solution of 4-(N,N)-dipheny-
laminostyrene14 (215 mg, 0.79 mmol) in xylenes (20 mL) was
added slowly and the temperature increased to 140 °C. This
mixture was stirred at 140 °C for a week. The solvents were
removed under vacuum, and the crude product dissolved in
methylene chloride and washed with water. After evaporation of
the solvents, the product is purified by column chromatography
(silica, methylene chloride) to give 9 in 11% yield as a yellow
solid (42 mg). 1H NMR (400 MHz, CDCl3, 25 °C): δ 7.86 (s, 4H),
7.56 (s, 8H), 7.42 (d, 4H, J=8.77), 7.30-7.25 (m, 12H), 7.14-
7.00 (m, 16H), 1.30-1.18 (m, 16H), 0.89-0.77 (m, 8H), 0.79 (t,
Theoretical Calculations. Molecular orbital (MO) calcula-
tions were computed using the semiempirical quantum chemistry