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H. Xiao et al. / Polymer 53 (2012) 2873e2883
poured into methanol. The precipitated polymer was recovered by
filtration and purified by silica column chromatography with
toluene to remove small molecular complex and catalyst residue.
(br, CH3). Element Anal. Calcd (%): C, 89.00; H, 9.87; S, 0.39; N,
0.34; Found (%): C, 88.93; H, 9.91; S, 0.42; N, 0.39.
1H NMR (300 MHz, CDCl3)
d(ppm): 7.86 (br, ArH), 7.70 (br, ArH),
4.1.2.10. PF-G210. Monomer 1 (219.2 mg, 0.40 mmol), 2 (321 mg,
0.50 mmol) and 5 (95.2 mg, 0.10 mmol). 1H NMR (300 MHz, CDCl3)
7.50 (br, ArH), 7.20e7.16 (br, ArH), 2.64 (br, CH2), 2.14 (br, CH2),
1.46e1.02 (br, CH2), 0.86e0.83 (br, CH3). Element Anal. Calcd (%): C,
88.89; H, 9.96; S, 0.40; N, 0.35; Found (%): C, 88.75; H, 9.85; S, 0.42;
N, 0.39.
d(ppm): 7.83 (br, ArH), 7.68 (br, ArH), 7.36 (br, ArH), 7.15e6.98 (br,
ArH), 2.63 (br, CH2), 2.11 (br, CH2), 1.25e1.02 (br, CH2), 0.82e0.75
(br, CH3). Element Anal. Calcd (%): C, 88.38; H, 9.48; S, 0.74; N,
0.65; Found (%): C, 88.31; H, 9.54; S, 0.67; N, 0.74.
4.1.2.2. PF-G11. Monomer 1 (268.5 mg, 0.49 mmol), 2 (321 mg,
0.50 mmol) and 4 (8.2 mg, 0.01 mmol). 1H NMR (300 MHz, CDCl3)
4.1.2.11. PF-SO10-G25. Monomer
(321 mg, 0.50 mmol), 3 (37.4 mg, 0.10 mmol) and 5 (47.6 mg,
0.05 mmol). 1H NMR (300 MHz, CDCl3)
(ppm): 8.19(br, ArH),
8.00(br, ArH), 7.85(br, ArH), 7.68(br, ArH), 7.50(br, ArH),
7.16e7.14(br, ArH), 2.63(br, CH2), 2.12(br, CH2), 1.46e1.02 (br, CH2),
0.82e0.80 (br, CH3). Element Anal. Calcd (%): C, 87.75; H, 9.44; S,
1.23; N, 0.36; Found (%): C, 87.70; H, 9.56; S, 1.20; N, 0.39.
1 (191.8 mg, 0.35 mmol), 2
d(ppm): 7.86 (br, ArH), 7.70 (br, ArH), 7.50 (br, ArH), 7.20e7.16 (br,
ArH), 2.64 (br, CH2), 2.15 (br, CH2), 1.46e1.02 (br, CH2), 0.86e0.83
(br, CH3). Element Anal. Calcd (%): C, 89.60; H, 10.07; S, 0.08; N,
0.07; Found (%): C, 89.34; H, 10.20; S, <0.3; N, <0.3.
d
4.1.2.3. PF-G110. Monomer 1 (219.2 mg, 0.40 mmol), 2 (321 mg,
0.50 mmol) and 4 (82 mg, 0.10 mmol). 1H NMR (300 MHz, CDCl3)
d
(ppm): 7.86 (br, ArH), 7.70 (br, ArH), 7.50 (br, ArH), 7.20e7.16 (br,
4.1.2.12. PF-SO15-G25. Monomer
(321 mg, 0.50 mmol), 3 (56.1 mg, 0.15 mmol) and 5 (47.6 mg,
0.05 mmol). 1H NMR (300 MHz, CDCl3)
(ppm): 8.19 (br, ArH), 8.00
(br, ArH), 7.85 (br, ArH), 7.68 (br, ArH), 7.50 (br, ArH), 7.16e7.14 (br,
ArH), 2.63 (br, CH2), 2.12 (br, CH2), 1.46e1.02 (br, CH2), 0.82e0.80
(br, CH3). Element Anal. Calcd (%): C, 87.08; H, 9.21; S, 1.68; N,
0.37; Found (%): C, 87.01; H, 9.31; S, 1.74; N, 0.42.
1 (164.4 mg, 0.30 mmol), 2
ArH), 2.65 (br, CH2), 2.14 (br, CH2), 1.46e1.02 (br, CH2), 0.86e0.83
(br, CH3). Element Anal. Calcd (%): C, 88.15; H, 9.63; S, 0.77; N,
0.67; Found (%): C, 88.26; H, 9.72; S, 0.72; N, 0.70.
d
4.1.2.4. PF-G115. Monomer 1 (191.8 mg, 0.35 mmol), 2 (321 mg,
0.50 mmol) and 4 (123 mg, 0.15 mmol). 1H NMR (300 MHz, CDCl3)
d(ppm): 7.86 (br, ArH), 7.70 (br, ArH), 7.50 (br, ArH), 7.20e7.16 (br,
ArH), 2.66 (br, CH2), 2.14 (br, CH2), 1.46e1.02 (br, CH2), 0.86e0.83
(br, CH3). Element Anal. Calcd (%): C, 87.49; H, 9.33; S, 1.12; N,
0.98; Found (%): C, 87.28; H, 9.45; S, 1.29; N, 1.05.
4.1.2.13. PF-SO20-G25. Monomer
(321 mg, 0.50 mmol), 3 (74.8 mg, 0.20 mmol) and 5 (47.6 mg,
0.05 mmol). 1H NMR (300 MHz, CDCl3)
(ppm): 8.20 (br, ArH), 8.00
1 (137.0 mg, 0.25 mmol), 2
d
(br, ArH), 7.85 (br, ArH), 7.71 (br, ArH), 7.50 (br, ArH), 7.16e7.14 (br,
ArH), 2.63 (br, CH2), 2.12 (br, CH2), 1.46e1.02 (br, CH2), 0.82e0.80
(br, CH3). Element Anal. Calcd (%): C, 86.38; H, 8.33; S, 2.14; N,
0.37; Found (%): C, 86.44; H, 8.45; S, 2.21; N, 0.44.
4.1.2.5. PF-SO10-G15. Monomer
(321 mg, 0.50 mmol), 3 (37.4 mg, 0.10 mmol) and 4 (41 mg,
0.05 mmol). 1H NMR (300 MHz, CDCl3)
(ppm): 8.21 (br, ArH), 8.00
1 (191.8 mg, 0.35 mmol), 2
d
(br, ArH), 7.86 (br, ArH), 7.73 (br, ArH), 7.50 (br, ArH), 7.20e7.14 (br,
ArH), 2.66 (br, CH2), 2.15 (br, CH2), 1.46e1.02 (br, CH2), 0.86e0.83
(br, CH3). Element Anal. Calcd (%): C, 87.61; H, 9.53; S, 1.25; N,
0.36; Found (%): C, 87.15; H, 9.64; S, 1.38; N, 0.40.
4.2. Instrumentation
1H and 13C NMR spectra were recorded on a Bruker DRX-400
spectrometer operating respectively in deuterated chloroform or
dimethylsulfoxide solution with tetramethylsilane as a reference.
Mass (MS) experiments were performanced on a Bruker Esquire
HCT Plus. The molecular weight of the polymers was determined by
Waters GPC 2410 in THF. Number-average (Mn) and weight-average
(Mw) molecular weights were estimated by using a calibration
curve of polystyrene standards. Elemental analyses were per-
formed on Vario EL Elemental Analysis Instrument (Elementar Co.).
Thermogravimetric analysis (TGA) measurements were performed
on Netzsch TG 209 under N2 at a heating rate of 20 ꢁC/min. UVeVis
absorption spectra were recorded on an HP 8453 spectrophotom-
eter. The PL spectra were obtained on a Jobin Yvon Fluorolog-3
spectrofluorometer. Cyclic voltammetry (CV) was recorded on
a computer-controlled CHI660A electrochemical workstation. The
thin polymer film was coated on a platinum electrode as a working
electrode at a scan rate of 50 mV/s against calomel reference elec-
trode in a nitrogen-saturated solution of 0.1 M tetrabutylammonium
hexafluorophosphate (Bu4NPF6) in acetonitrile (CH3CN). A Pt wire
was used as the counter electrode. HOMO levels were calculated
according to an empirical formula (EHOMO ¼ ꢀe(Eox þ 4.4) (eV)) with
the ferrocene oxidation potential as the standard for the vacuum
energy level. The optical band gaps (Eg) of polymers were calcu-
lated according to the formula Eg ¼ 1241/lonset, in which lonset
was the absorption edge of the film. The PL quantum yields
were measured using an Integrating Sphere IS080 (LabSphere)
to collect the emitted light in all directions under the excitation
of 325 nm line of a HeCd laser (Melles Griot). The thicknesses
of the solid films, typically, were 100e200 nm. The current
4.1.2.6. PF-SO15-G15. Monomer
(321 mg, 0.50 mmol), 3 (56.1 mg, 0.15 mmol) and 4 (41 mg,
0.05 mmol). 1H NMR (300 MHz, CDCl3)
(ppm): 8.21 (br, ArH), 8.00
1 (164.4 mg, 0.30 mmol), 2
d
(br, ArH), 7.86 (br, ArH), 7.73 (br, ArH), 7.47 (br, ArH), 7.20e7.14 (br,
ArH), 2.64 (br, CH2), 2.15 (br, CH2), 1.46e1.02 (br, CH2), 0.86e0.83
(br, CH3). Element Anal. Calcd (%): C, 86.92; H, 9.29; S, 1.70; N,
0.37; Found (%): C, 86.59; H, 9.43; S, 1.87; N, 0.39.
4.1.2.7. PF-SO20-G15. Monomer 1 (137 mg, 0.25 mmol), 2 (321 mg,
0.50 mmol), 3 (74.8 mg, 0.20 mmol) and 4(41 mg, 0.05 mmol). 1H
NMR (300 MHz, CDCl3) d(ppm): 8.20 (br, ArH), 8.00 (br, ArH), 7.86
(br, ArH), 7.73 (br, ArH), 7.47 (br, ArH), 7.20e7.14 (br, ArH), 2.64 (br,
CH2), 2.15 (br, CH2), 1.46e1.02 (br, CH2), 0.86e0.83 (br, CH3).
Element Anal. Calcd (%): C, 86.21; H, 9.05; S, 2.18; N, 0.38; Found
(%): C, 86.43; H, 8.95; S, 2.28; N, 0.41.
4.1.2.8. PF-G21. Monomer 1 (268.5 mg, 0.49 mmol), 2 (321 mg,
0.50 mmol) and 5 (9.5 mg, 0.01 mmol). 1H NMR (300 MHz, CDCl3)
d(ppm): 7.83 (br, ArH), 7.68 (br, ArH), 7.36 (br, ArH), 7.15e6.98 (br,
ArH), 2.63 (br, CH2), 2.16 (br, CH2), 1.25e1.02 (br, CH2), 0.82e0.75
(br, CH3). Element Anal. Calcd (%): C, 89.55; H, 10.22; S, 0.08; N,
0.07; Found (%): C, 89.50; H, 10.30; S, <0.3; N, <0.3.
4.1.2.9. PF-G25. Monomer 1 (246.6 mg, 0.45 mmol), 2 (321 mg,
0.50 mmol) and 5 (47.6 mg, 0.05 mmol). 1H NMR (300 MHz, CDCl3)
d(ppm): 7.83 (br, ArH), 7.68 (br, ArH), 7.36 (br, ArH), 7.15e6.98 (br,
ArH), 2.63 (br, CH2), 2.12 (br, CH2), 1.25e1.02 (br, CH2), 0.82e0.75