Kim So-Yoen, Lee Ah-Rang, Jin Guo Fan, Cho Yang-Jin, Son Ho-Jin, Han Won-Sik, Kang Sang Ook
†Department of Advanced Materials Chemistry, Korea University, Sejong 339-700, South Korea.
‡Department of Chemistry, Seoul Women's University, Seoul 139-774, South Korea.
J Org Chem. 2015 May 1;80(9):4573-80. doi: 10.1021/acs.joc.5b00336. Epub 2015 Apr 16.
We studied electronic change in oligothiophenes by employing o-carborane into a molecular array in which one or both end(s) were substituted by electron-withdrawing dicyano-vinyl group(s). Depending on mono- or bis-substitution at the o-carborane, a series of linear A1-D-A2 (1a-1c) or V-shaped A1-D-A2-D-A1 (2a-2c) oligothiophene chain structures of variable length were prepared; A1, D, and A2, represent dicyano-vinyl, oligothiophenyl, and o-carboranyl groups, respectively. Among this series, 2a shows strong electron-acceptor capability of o-carborane comparable to that of the dicyano-vinyl substituent, which can be elaborated by a conformational effect driven by cage σ*-π* interaction. As a result, electronic communications between o-carborane and dicyano-vinyl groups are successfully achieved in 2a.
我们通过将邻碳硼烷引入分子阵列来研究低聚噻吩中的电子变化，该分子阵列的一端或两端被吸电子的二氰基乙烯基取代。根据邻碳硼烷上的单取代或双取代情况，制备了一系列长度可变的线性A1-D-A2（1a - 1c）或V形A1-D-A2-D-A1（2a - 2c）低聚噻吩链结构；A1、D和A2分别代表二氰基乙烯基、低聚噻吩基和邻碳硼烷基团。在该系列中，2a显示出邻碳硼烷具有与二氰基乙烯基取代基相当的强电子受体能力，这可以通过笼状σ*-π*相互作用驱动的构象效应来解释。结果，在2a中成功实现了邻碳硼烷和二氰基乙烯基之间的电子通信。
