Branched polythiophenes by Ni-catalyzed Kumada coupling

Branched polythiophenes by Ni-catalyzed Kumada coupling
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Ni 催化 Kumada 偶联制备支化聚噻吩

DOI:
10.1039/c4py00899e
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发表时间:
2014
期刊:
影响因子:
4.6
通讯作者:
Ludwigs S
Ludwigs S
中科院分区:
化学2区
文献类型:
--
作者:
Scheuble M;Richter TV;Goll M;Link S;López- Navarrete JT;Ruff A;Ruiz-Delgado MC;Ludwigs S

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以5,5 " -二溴-2,2 ':3 ',2 " -噻吩(3TBr2)和5,5 ',5 " -三溴-2,2 ':3 ',2 " -噻吩(3TBr3)为原料,采用镍催化Kumada型偶联原位合成支化AB2单体,控制了支化多噻吩的合成。与标准的氧化聚合程序相比,获得具有相当高分子量的高支化聚合物结构是这种一锅聚合的关键优势。我们的合成路线进一步允许原位端基功能化,例如戊烯功能化的支链多噻吩,从而易于获得具有定制性能的支链多噻吩。特别是,光学性质的比较可以得出关于所获得的材料相对于线性和全分支系统的结构的结论。能级是通过循环伏安法测量薄膜得到的。DFT计算为解释聚合物可能的分子结构(即分支密度)与其性质的关系提供了进一步的指导。
The controlled synthesis of branched polythiophenes via Ni-catalyzed Kumada type coupling of branched AB2 monomers prepared in situ from 5,5′′-dibromo-2,2′:3′,2′′-terthiophene (3TBr2) and 5,5′,5′′-tribromo-2,2′:3′,2′′-terthiophene (3TBr3) is presented. The access to highly branched polymer architectures with rather high molecular weights is a key benefit of this one-pot polymerization with respect to standard oxidative polymerization procedures. Our synthetic route further allows the in situ endgroup functionalization as shown exemplarily for pentene functionalized branched polythiophenes and eases thereby the access to branched polythiophenes with tailor-made properties. In particular a comparison of the optical properties allows conclusions about the architecture of the obtained materials with respect to linear and fully branched systems. Energy levels are obtained by cyclic voltammetry measurements in thin films. DFT calculations provide further guidance on the interpretation of the possible molecular structure of the polymer (i.e. branching density) in correlation with their properties.
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