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3 for poly-la, poly-lb, and poly-lc, respectively, as determined by gel permeation chromatography (GPC) using chloroform as the eluent. Relatively low molecular weights of these polymers may be due to precipitation in solvents during polymerization. The >H NMR spectrum of poly-la in CDCb showed a sharp singlet centered at 6.84 ppm due to the thiophene ring proton at the 4-position, indicating that the polymer possesses a highly HT regioregular structure. On the contrary, the 'H NMR spectrum of poly-lb prepared with the CuO-modified Stille method showed rather broad resonances due to contamination with a small amount of paramagnetic Cu(II) ion used as a cocatalyst during the polymerization. After removal of the Cu(II) ion by extraction with aqueous ethylenediaminetetraacetic acid (EDTA), the resonances became sharper. Standard titration experiments12 using sodium diethyldithiocarbamate suggest that the poly-lb contains 0.2 equiv of Cu(II) ion to a monomer unit of poly-lb.
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38
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85037456134
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note
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2 caused a significant red shift of the π-π transition of over 300 nm, and therefore, this possibility may also be excluded. (Figure Presented)
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