Synthesis and properties of novel π-conjugated polymers by cycloaddition polymerization of bisthioketenes

由对共轭二炔驱动的醛硫烯酮与其烷硫醇互变异构体发生环加成反应，合成了主链上含给电子二硫富烯单元的π共轭聚合物。这些聚合物与四氰基喹甲烷形成了可溶的电荷转移络合物。由杂芳基二炔(2，5-二乙炔基噻吩基、2，5-二乙炔基-3-己基噻吩基和2，5-二乙炔基-3-己基吡啶)衍生的醛硫酮与其烷基硫醇互变异构体进行环加成反应，合成了主链上含有给电子型二硫代亚硫烯单元和典型杂芳烃(噻吩基或吡啶)单元的π共轭聚合物。聚合物的UV-Vis吸收光谱表明，聚合物中的p-共轭体系比以前报道的由1，4-二乙基苯制得的聚合物更有效地膨胀。通过π的环加成聚合，合成了氧化还原活性交替的二茂铁与二硫代富烯共聚物…从1，1‘-双(三甲基硅乙烯基)二茂铁中衍生出更多的硫代烯酮。由于单元结构中的有效相互作用，聚合物的循环伏安图只显示一个可逆的电位。以5，5-二乙炔基-2，2-联吡啶为原料，通过环加成反应合成了一种含二硫富烯单元和联吡啶单元的π共轭聚合物。UV-Vis吸收光谱表明，与由1，4-二乙基苯制得的二硫代富烯的苯类似物相比，该聚合物的π-偶联体系更有效地膨胀。循环伏安测试表明，二硫富烯-联吡啶聚合物是比苯类似物更弱的电子给体聚合物。这些结果一致认为，在共轭聚二硫富烯中引入接受电子的联吡啶基团引起了分子内电荷转移(CT)效应。我们以2，4-二亚甲基-L，3-二硫杂环乙烷为单元，通过环加成聚合反应合成了含2，4-二亚甲基-L，3-二硫杂环乙烷单元的π共轭聚合物。聚合物的电学性质表明，这些聚合物比聚二硫富烯S具有更强的电子给体作用。我们合成了二硅基取代的硫酮二聚体，并证明了有效的S-p共轭包括从二硫杂环己烯二聚体到硅-硅单元的独特的电荷转移即使硅-硅单元通常充当电子给体。较少

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