Souto Manuel, Calbo Joaquín, Ratera Imma, Ortí Enrique, Veciana Jaume
Institut de Ciència de Materials de Barcelona (ICMAB-CSIC)/CIBER-BBN, Campus Universitari de la UAB, 08193, Bellaterra, Spain.
Instituto de Ciencia Molecular, Universidad de Valencia, 46980, Paterna, Spain.
Chemistry. 2017 Aug 16;23(46):11067-11075. doi: 10.1002/chem.201701623. Epub 2017 Jul 31.
Three conjugated donor-π-acceptor radical systems (1 a-1 c) were prepared by bridging a tetrathiafulvalene (TTF) electron-donor unit to a polychlorotriphenylmethyl (PTM) electron-acceptor radical through vinylene units of different lengths. The dependence of the intramolecular charge transfer on the length of the conjugated bridge has been analyzed by different electrochemical and spectroscopic techniques. Linear optical properties and the second-order nonlinear optical (NLO) response of these derivatives have been computed by comparing systems 1 a-1 c with the non-radical analogues (2 a-2 c). Interestingly, an enhanced NLO response is predicted for dyads 1 a-1 c with PTM in the radical form and for compounds with longer vinylene bridges. Calculations confirm the active role the bridge plays for electronic communication between the donor TTF and the acceptor PTM units.
通过不同长度的亚乙烯基单元将四硫富瓦烯（TTF）电子供体单元与聚氯三苯甲基（PTM）电子受体自由基相连，制备了三种共轭供体-π-受体自由基体系（1 a - 1 c）。已通过不同的电化学和光谱技术分析了分子内电荷转移对共轭桥长度的依赖性。通过将体系1 a - 1 c与非自由基类似物（2 a - 2 c）进行比较，计算了这些衍生物的线性光学性质和二阶非线性光学（NLO）响应。有趣的是，预测自由基形式的含PTM的二元体系1 a - 1 c以及具有更长亚乙烯基桥的化合物具有增强的NLO响应。计算证实了桥在供体TTF和受体PTM单元之间的电子通信中所起的积极作用。
