Study of Cross-Coupling Reactions for Precisely Controlled Synthesis of π-Conjugated Polymers

乙烯烯键完全顺式控制的全顺式聚苯乙烯（pav）具有优异的成膜性能，并在薄膜中发生光诱导不溶化和顺式到反式异构化，使全反式pav具有良好的载流子迁移率，最高可达3.5×10^<-2> cm^2 V^<-1> s^<-1>。基于对钯催化交叉偶联反应基本过程的详细机理研究，开发了高选择性合成全顺式和全反式pav的方法。通过定量的方法阐明了光诱导pav不溶化所需的聚合物的主要结构。建立了一种新的催化体系，将2-溴-3-烷基噻吩转化为高度首尾相连的区域规则聚（3-烷基噻吩）s （HT-P3ATs）。

All-cis poly (arylene vinylene) s (PAVs) with the vinylene linkages entirely controlled to cis geometry possess an excellent film-forming property, and undergo photo-induced insolubilization along with cis-to-trans isomerization in thin films, giving all-trans PAVs with good charge-carrier mobility up to 3.5×10^<-2> cm^2 V^<-1> s^<-1>. Highly selective ways of synthesizing all-cis and all-trans PAVs have been developed based on detailed mechanistic studies of elementary processes of palladium-catalyzed cross-coupling reactions. The primary structures of polymers that are required for the photo-induced insolubilization of PAVs have been elucidated by a quantitative method. A novel catalytic system that converts 2-bromo-3-alkylthiophenes to highly head-to-tail regioregular poly (3-alkylthiophene) s (HT-P3ATs) has been developed.