3-(N-烷基氨基)噻吩的电化学研究：氧化聚合独特机制的实验和理论见解。

Electrochemical study of 3-(N-alkylamino)thiophenes: experimental and theoretical insights into a unique mechanism of oxidative polymerization.

机构信息

Department of Chemistry and Molecular Biology, North Dakota State University, NDSU Dept. 2735, P.O. Box 6050, Fargo, North Dakota 58108-6050, USA.

出版信息

J Phys Chem B. 2010 Apr 29;114(16):5275-82. doi: 10.1021/jp912287s.

DOI:10.1021/jp912287s

PMID:20359205

Abstract

A number of conjugated polymer systems can be generated via electropolymerization, including polythiophenes and polyanilines. While both have been reported to polymerize anodically via radical coupling, the presence of the aniline nitrogen plays a significant role in the mechanism of electropolymerization. In this study, the electropolymerization mechanism of 3-(N-alkylamino)thiophenes, structural hybrids of thiophene and aniline, is studied utilizing experimental and theoretical methods. Synthesis of new short chain 3-(N-alkylamino)thiophenes is discussed, and a mechanism of electropolymerization is proposed whereby oxidation occurs through removal of a nitrogen lone pair electron, followed by a chemical step resulting in radical contribution at the 2-position of the thiophene ring. Coupling of these final radical cations thus results in a typical poly(alpha-alpha'-thiophene) backbone.

摘要

许多共轭聚合物体系可以通过电化学聚合来生成，包括聚噻吩和聚苯胺。尽管两者都已被报道可以通过自由基偶联阳极聚合，但苯胺氮的存在在电化学聚合的机制中起着重要作用。在这项研究中，利用实验和理论方法研究了 3-(N-烷基氨基)噻吩的电化学聚合机制，噻吩和苯胺的结构杂合体。讨论了新的短链 3-(N-烷基氨基)噻吩的合成，并提出了一种聚合机制，其中通过去除氮孤对电子发生氧化，随后发生化学步骤，导致噻吩环 2 位的自由基贡献。这些最终的自由基阳离子的偶联导致典型的聚（α-α'-噻吩）主链。