Direct Arylation Polycondensation of Bithiazole Derivatives with Various Acceptors
Direct Arylation Polycondensation of Bithiazole Derivatives with Various Acceptors
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DOI：
10.1021/ma5014397
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发表时间：
2014-11-11
期刊：
影响因子：
5.5
通讯作者：
Kanbara, Takaki
中科院分区：
文献类型：
--
作者：
Kuramochi, Masahiro;Kuwabara, Junpei;Kanbara, Takaki
通过钯催化的直接芳基化缩聚反应，合成了含有联噻唑单元和不同受体单元的新型PI共轭聚合物。缩聚反应的结果取决于单体中的硫族元素。Se原子的存在抑制了聚合，可能是由于Se部分与Pd中心配位；通过提高反应温度(120℃)解决了这个问题。硫族元素也影响所得聚合物的链间相互作用。较强的链间相互作用导致了较低的溶解度、较高的结晶度和较大的吸收红移。吸收光谱和密度泛函理论计算表明，如果双噻唑单元与强受体单元直接相连，则双噻唑单元为弱给体单元。双噻唑单元与强受体单元的结合提供了较深的HOMO-LUMO能级。
Novel pi-conjugated polymers with a bithiazole unit and various acceptor units were synthesized by polycondensation via Pd-catalyzed direct arylation. The results of polycondensation reactions depend on chalcogen elements in the monomers. The presence of a Se atom inhibited polymerization, presumably owing to the coordination of the Se moiety to the Pd center; the issue was resolved by increasing the reaction temperature (120 degrees C). The chalcogen elements also affected the interchain interactions of the obtained polymers. The strong interchain interactions led to low solubility, high crystallinity, and a large red-shift of absorption in the film state compared with that in the solution state. Absorption spectra and DFT calculations revealed that the bithiazole units served as weak donor units in case that the bithiazole units were directly connected to strong acceptor units. The combination of the bithiazole units with the strong acceptor units afforded deep HOMO-LUMO levels.