L. Li et al. / Journal of Organometallic Chemistry 696 (2011) 1189e1197
1191
n-hexane/CH2Cl2 (1:1, v/v) to provide L0-2TMS (56 mg, 34%) as
deep yellow solid. IR (KBr): (C]O) 1678, 1593, (C^C)
2160 cmꢀ1 1H NMR (400 MHz, CDCl3):
¼ 8.36 (d, J ¼ 1.4 Hz, 2H,
Ar), 8.23 (d, J ¼ 8.0 Hz, 2H, Ar), 7.83 (dd, J ¼ 1.4, 8.0 Hz, 2H, Ar), 0.29
(s, 18H, Si(CH3)3) ppm. 13C NMR (100 MHz, CDCl3):
182.18 (C]O), 137.32, 133.54, 132.83, 131.12, 129.82, 127.66 (Ar),
103.43,100.71 (C^C), 0.08 (Si(CH3)3) ppm. FAB-MS (m/z): 401. Anal.
Calc. for C24H24O2Si2: C, 71.95; H, 6.04. Found: C, 71.78; H, 6.34%.
ionic impurities and catalyst residue. After removal of the solvent,
the crude product was washed with hexane (3 ꢂ 15 mL) followed
by methanol (3 ꢂ15 mL) and drying in vacuo to obtain P0 (60 mg,
38%) as an orange solid.
a
n
n
.
d
d
¼ 182.30,
Spectral Data: IR (KBr):
n
(C]O) 1673, 1586,
d
n
(C^C) 2085 cmꢀ1
¼ 8.16e8.12 (m, 4H, Ar), 7.59 (d,
.
1H NMR (400 MHz, CDCl3):
J ¼ 6.9 Hz, 2H, Ar), 2.17e2.13 (m,12H, PCH2C3H7),1.65e1.62 (m,12H,
PCH2CH2C2H5), 1.52e1.43 (m, 12H, PCH2CH2CH2CH3), 0.99 (t,
J ¼ 7.2 Hz, 18H, PCH2CH2CH2CH3) ppm. 31P NMR (161 MHz, CDCl3):
2.3.4. Synthesis of L1-2TMS
It was prepared following the same procedures as for L0-2TMS
but L1-2Br was used instead.
d
¼ 3.52 (1JPꢀPt ¼ 2307 Hz) ppm. Anal. Calc. for (C42H60O2P2Pt)n: C,
59.07; H, 7.08. Found: C, 59.35; H, 7.29%. GPC (THF): Mw ¼ 12980,
Mn ¼ 7270, DP ¼ 9, PDI ¼ 1.78.
Orange solid (86%). Spectral Data: IR (KBr):
n
d
(C]O) 1675, 1593,
¼ 8.44 (d, J ¼ 1.9 Hz,
n
P1: Red solid (77%). Spectral Data: IR (KBr):
n(C]O) 1672, 1595,
n
(C^C) 2142 cmꢀ1. 1H NMR (400 MHz, CDCl3):
(C^C)2081 cmꢀ1.1H NMR (400 MHz, CDCl3):
d
¼ 8.43(s, 2H, Ar), 8.26
2H, Ar), 8.27 (d, J ¼ 8.2 Hz, 2H, Ar), 7.77 (dd, J ¼ 1.9, 8.2 Hz, 2H, Ar),
7.34 (s, 2H, Ar), 2.71 (t, J ¼ 7.5 Hz, 4H, C5H11CH2) 1.72e1.65
(m, 4H, C4H9CH2CH2), 1.40e1.34 (m, 12H, CH3C3H6CH2CH2), 0.91
(t, J ¼ 6.9 Hz, 6H, CH3C3H6CH2CH2), 0.28 (s, 18H, Si(CH3)3) ppm.
(d, J ¼ 8.1 Hz, 2H, Ar), 7.88 (d, J ¼ 8.1 Hz, 2H, Ar), 7.36 (s, 2H, Ar), 2.71
(br, 4H, alkyl), 2.18 (br, 12H, alkyl), 1.63 (br, 16H, alkyl), 1.54e1.49 (m,
12H, alkyl), 1.36 (br, 12H, alkyl), 0.98 (t, J ¼ 7.1 Hz, 18H, alkyl), 0.92 (t,
J ¼ 6.8 Hz, 6H, alkyl) ppm. 31P NMR (161 MHz, CDCl3):
d
¼ 3.69
13C NMR (100 MHz, CDCl3):
d
¼ 183.17, 181.94 (C]O), 150.66, 141.61,
(1JPꢀPt ¼ 2333 Hz) ppm. Anal. Calc. for (C62H88O2P2S2Pt)n: C, 62.76; H,
7.48. Found: C, 62.98; H, 7.54%. GPC (THF): Mw ¼ 61,040, Mn ¼ 16,250,
DP ¼ 14, PDI ¼ 3.76.
139.65, 134.31, 132.45, 130.78, 128.63, 126.94, 123.95, 120.77 (Ar),
103.79, 97.28 (C^C), 31.91, 30.37, 30.02, 29.26, 22.95, 14.46 (C6H13),
0.25 (Si(CH3)3) ppm. FAB-MS (m/z): 733. Anal. Calc. for C44H52O2S2Si2:
C, 72.08; H, 7.15. Found: C, 72.12; H, 7.01%.
2.3.7. Synthesis of platinum model complexes M0eM1
All of them were synthesized following the dehydrohalogenat-
ing coupling between trans-[PtCl(Ph)(PEt3)2] [47] and the corre-
sponding diterminal alkynes. A typical procedure was given for M0
starting from L0.
To a stirred mixture of ligand L0 (7 mg, 0.03 mmol) and two
molar equivalents of trans-[PtCl(Ph)(PEt3)2] (31 mg, 0.06 mmol) in
NEt3 (10 mL) and CH2Cl2 (10 mL), CuI (3 mg) was added as the
catalyst. The solution was stirred at room temperature for 15 h
under nitrogen, after which all volatile components were removed
under vacuum. The crude product was taken up in CH2Cl2 and
purified on preparative silica TLC plates with a mixture of n-
hexane/ethyl acetate (5:1, v/v) as eluent. A deep yellow band con-
sisting of M0 was obtained as a yellow solid (24 mg, 70%).
2.3.5. Synthesis of L0eL1
The diethynyl ligands were prepared by the desilylation of each
of the TMS derivatives. A typical procedure was given for L0 starting
from L0-2TMS.
A mixture of L0-2TMS (84 mg, 0.21 mmol) and K2CO3 (61 mg,
0.44 mmol) in a solution mixture of methanol (6 mL) and CH2Cl2
(15 mL), under a nitrogen atmosphere, was stirred at room
temperature overnight. The solvents were removed on a rotary
evaporator in vacuo. The crude product was purified by column
chromatography on silica gel eluting with n-hexane/CH2Cl2 (1:1, v/
v) to provide L0 (48 mg, 91%) as a deep yellow solid.
Spectral Data: IR (KBr):
n
(C]O) 1673, 1593,
n
(C^C) 2109,
n
(C^CH) 3272 cmꢀ1 1H NMR (400 MHz, CDCl3):
.
d
¼ 8.40 (d,
Spectral Data: IR (KBr):
n(C]O) 1672, 1587, n .
(C^C) 2092 cmꢀ1
J ¼ 1.6 Hz, 2H, Ar), 8.27 (d, J ¼ 8.0 Hz, 2H, Ar), 7.88 (dd, J ¼ 1.6,
1H NMR (CDCl3):
d
¼ 8.14e8.10 (m, 4H, Ar), 7.61 (dd, J ¼ 1.9, 8.2 Hz,
8.0 Hz, 2H, Ar), 3.38 (s, 2H, C^CH) ppm. 13C NMR (100 MHz, CDCl3):
2H, Ar), 7.38e7.29 (m, 4H, Ar), 7.00e6.97 (m, 4H, Ar), 6.84e6.80 (m,
2H, Ar), 1.79e1.74 (m, 24H, PCH2CH3), 1.16e1.08 (m, 36H, PCH2CH3)
d
¼ 181.75, 181.70 (C]O), 137.31, 133.24, 132.80, 130.97, 128.52,
127.43 (Ar), 82.13, 81.93 (C^C) ppm. FAB-MS (m/z): 256. Anal. Calc.
ppm. 13C NMR (CDCl3):
d
¼ 184.55, 182.75 (C]O), 139.29, 136.35,
for C18H8O2: C, 84.37; H, 3.15. Found: C, 84.20; H, 3.34%.
135.78, 133.78, 130.17, 129.24, 127.77, 127.40, 125.36, 121.80 (Ar),
L1: Orange solid (97%). Spectral Data: IR (KBr):
n(C]O) 1673,1596,
111.24 (C^C), 15.43, 8.38 (PEt3). 31P NMR (CDCl3):
d
¼ 10.07 ppm
n(C^C) 2096,
n
(C^CH) 3296 cmꢀ1 1H NMR (400 MHz, CDCl3):
.
(1JPtꢀP ¼ 2622 Hz). FAB-MS: m/z ¼ 1271 (Mþ). Anal. Calc. for
d
¼ 8.43 (d, J ¼ 1.9 Hz, 2H, Ar), 8.27 (d, J ¼ 8.2 Hz, 2H, Ar), 7.90 (dd,
C54H76O2P4Pt2: C, 51.02; H, 6.03. Found: C, 51.21; H, 6.23%.
J ¼ 1.9, 8.2 Hz, 2H, Ar), 7.35 (s, 2H, Ar), 3.58 (s, 2H, C^CH), 2.73 (t,
J ¼ 7.6 Hz, 4H, C5H11CH2), 1.71ꢀ1.64 (m, 4H, C4H9CH2CH2), 1.41e1.33
(m, 12H, CH3C3H6CH2CH2), 0.91 (t, J ¼ 6.9 Hz, 6H, CH3C3H6CH2CH2)
M1: Red solid (65%). Spectral Data: IR (KBr):
n
(C]O) 1672, 1592,
n
(C^C) 2080 cmꢀ1. 1H NMR (CDCl3):
d
¼ 8.41 (d, J ¼ 1.9 Hz, 2H, Ar),
8.24 (d, J ¼ 8.1 Hz, 2H, Ar), 7.88 (dd, J ¼ 1.9, 8.1 Hz, 2H, Ar), 7.35e7.32
(m, 6H, Ar), 7.00e6.96 (m, 4H, Ar), 6.84e6.80 (m, 2H,
Ar), 2.70 (t, J ¼ 7.7 Hz, 4H, C5H11CH2), 1.80e1.66 (m, 28H, PCH2-
CH3 þ C4H9CH2CH2), 1.43e1.32 (m, 12H, CH3C3H6CH2CH2), 1.16e1.08
(m, 36H, PCH2CH3), 0.91 (t, J ¼ 6.9 Hz, 6H, CH3C3H6CH2CH2) ppm.
ppm. 13C NMR (100 MHz, CDCl3):
d
¼ 182.74, 181.57 (C]O), 150.63,
141.68, 139.16, 133.95, 132.19, 130.51, 128.30, 126.49, 123.66, 119.08
(Ar), 85.29, 76.29 (C^C), 31.60, 30.13, 29.65, 28.96, 22.60, 14.11
(C6H13) ppm. FAB-MS (m/z): 589. Anal. Calc. for C38H36O2S2: C, 77.51;
H, 6.16. Found: C, 77.34; H, 6.32%.
13C NMR (CDCl3):
136.29, 134.40, 131.55, 129.97, 128.58, 128.41, 127.74, 127.34, 123.15,
d
¼ 183.95, 182.15 (C]O), 143.96, 140.57, 139.40,
2.3.6. Synthesis of platinum acetylide polymers P0eP1
121.73 (Ar), 102.31 (C^C), 32.23, 30.95, 30.22, 29.77, 23.04, 15.50,
The polymers were prepared by the dehydrohalogenative
polycondensation between trans-[PtCl2(PBu3)2] [46] and each of
L0eL1. A typical procedure was given for P0 starting from L0.
To a stirred mixture of L0 (47 mg, 0.18 mmol) and trans-
[PtCl2(PBu3)2] (123 mg 0.18 mmol) in freshly distilled triethylamine
(8 mL) and CH2Cl2 (15 mL) solution was added CuI (3 mg). The
solution was stirred at room temperature for 24 h under a nitrogen
atmosphere. The solvents were removed on a rotary evaporator in
vacuo. The residue was redissolved in CH2Cl2 and filtered through
a short aluminium oxide column using the same eluent to remove
14.50, 8.39 (C6H13 þ PEt3). 31P NMR (CDCl3):
d
¼ 10.28
(1JPtꢀP ¼ 2630 Hz). FAB-MS: m/z ¼ 1604 (Mþ). Anal. Calc. for
C74H104O2P4Pt2S2: C, 55.42; H, 6.54. Found: C, 55.34; H, 6.72%.
2.4. Solar cell fabrication and characterization
The device structure was ITO/PEDOT:PSS/polymer:PCBM blend/
Al. The ITO glass substrates (10
U per square) were cleaned by
sonication in toluene, acetone, ethanol and deionized water, dried in
an oven, and then cleaned with UV ozone for 300 s. As-received