| Budget Amount *help |
¥4,100,000 (Direct Cost: ¥4,100,000)
Fiscal Year 2001: ¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 2000: ¥2,000,000 (Direct Cost: ¥2,000,000)
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| Research Abstract |
π-Conjugated Polymers having electron-donating dithiafulvene units in the main chain were prepared by the cycloaddition reaction of aldothioketenes drived from p-conjugated diynes with their alkynthiol tautomers. These polymers formed soluble charge-transfer complexes with tetracyanoquinodimethane.
π-Conjugated polymers having electron-donating dithiafulvene units and typical heteroaromatic (thiophene or pyridine) units in the main chain were prepared by the cycloaddition polymerization of aldothioketenes derived from heteroaromatic diynes (2,5-diethynylthiophene, 2,5-diethynyl-3-hexylthiophene and 2,5-diethynylpyridine) with their alkynethiol tautomers. The UV-vis absorption spectra of the polymers suggested that the p-conjugation systems in the polymers expanded more effectively than the polymer obtained from 1,4-diethynylbenzene reported previously. A redox active alternating π-conjugated copolymer of ferrocene with dithiafulvene was synthesized by cycloaddition polymerization of ald
… More
othioketene derived from 1,1'-bis(trimethylsilylethynyl)ferrocene The cyclic voltammogram of the polymer showed only one reversible potential due to effective interaction within the unit structure. A π-conjugated polymer containing a dithiafulvene unit and a bipyridyl unit was prepared by cycloaddition polymerization of aldothioketene derived from 5,5-diethynyl-2,2 -bipyridine. The UV-vis absorption spectra showed that the π-conjugation system of the polymer expanded more effectively than that of a benzene analogue of a poly(dithiafulvene) obtained from 1,4-diethynylbenzene. Cyclic voltammetry measurement indicated the dithiafulvene-bipyridyl polymer as a weaker electron donor polymer than the benzene analogue. These results agreed that the incorporation of the electron accepting bipyridyl moiety into the conjugated poly(dithiafulvene) induced an intramolecular charge-transfer (CT) effect between the units.
We have prepared π-conjugated polymers with the 2,4-diylidene-l,3-dithietane unit by cycloaddition polymerization of bis(thioketene)s derived from bis(phosphonium salt)s. The electric properties of the polymers indicated that the polymers acted as strong electron donor than the poly(dithiafulvene)s. We have synthesized disilyl-substituted thiketene dimmers and demonstrated that effective s-p conjugations include the unique charge transfer from the thioketene dimmer to the Si-Si units, even though the Si-Si unit usually acts as an electron donor. Less
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