Synthesis and Properties of π-Conjugated Poly(dithiafulvene)s by Cycloaddition Polymerization of Heteroaromatic Bisthioketenes
Synthesis and Properties of π-Conjugated Poly(dithiafulvene)s by Cycloaddition Polymerization of Heteroaromatic Bisthioketenes
复制标题
杂芳族双硫烯酮环加成聚合π-共轭聚二硫富烯的合成及性能
DOI：
10.1021/ma992181z
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发表时间：
2000
期刊：
影响因子：
5.5
通讯作者：
Y. Chujo
中科院分区：
文献类型：
--
作者：
K. Naka;T. Uemura;Y. Chujo
以杂芳二炔（2,5-二乙基噻吩、2,5-二乙基-3-己基噻吩和2,5-二乙基吡啶）及其炔硫醇互变异构体为原料，经环加成聚合制备了具有供电子二噻吩和典型杂芳（噻吩或吡啶）主链单元的π共轭聚合物(2)。所得聚合物可溶于DMSO和DMF。聚合物的结构经核磁共振氢谱和红外光谱证实。2的紫外-可见吸收光谱表明，聚合物中的π共轭体系比先前报道的1,4-二乙基苯得到的聚合物更有效地膨胀。由2,5-二乙基噻吩制备的2a的循环伏安分析表明，与2,6-二（2-噻吩基）-1,4-二噻吩(3)相比，二噻吩单元的氧化峰发生了阳极位移和展宽，这是由于2a中π共轭的有效扩展。所有聚合物2形成可溶的电荷转移co。
π-Conjugated polymers (2) 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 obtained polymers were soluble in DMSO and DMF. The structures of the polymers were confirmed by 1H NMR and IR spectra. The UV−vis absorption spectra of 2 suggested that the π-conjugation systems in the polymers expanded more effectively than the polymer obtained from 1,4-diethynylbenzene reported previously. The cyclic voltammetry analysis of 2a (prepared from 2,5-diethynylthiophene) showed an anodic shift and a broadening of the oxidation peak for the dithiafulvene unit compared with that of 2,6-bis(2-thienyl)-1,4-dithiafulvene (3), due to the effective expansion of the π-conjugation in 2a. All polymers 2 formed soluble charge-transfer co...