Shoji Taku, Maruyama Akifumi, Yaku Chisa, Kamata Natsumi, Ito Shunji, Okujima Tetsuo, Toyota Kozo
Department of Chemistry, Faculty School of Science, Shinshu University, Matsumoto 390-8621, Nagano (Japan), Fax: (+) 81-263-37-2476; Department of Material Science, Graduate School of Science and Technology, Shinshu University, Matsumoto 390-8621, Nagano (Japan).
Chemistry. 2015 Jan 2;21(1):402-9. doi: 10.1002/chem.201405004. Epub 2014 Nov 4.
Aryl-substituted 1,1,4,4-tetracyano-1,3-butadienes (FcTCBDs) and bis(1,1,4,4-tetracyanobutadiene)s (bis-FcTCBDs), possessing a ferrocenyl group on each terminal, were prepared by the reaction of a variety of alkynes with tetracyanoethylene (TCNE) in a [2+2] cycloaddition reaction, followed by retro-electrocyclization of the initially formed [2+2] cycloadducts (i.e., cyclobutene derivatives). The characteristic intramolecular charge transfer (ICT) between the donor (ferrocene) and acceptor (TCBD) moieties were investigated by using UV/Vis spectroscopy. The redox behaviors of FcTCBDs and bis-FcTCBDs were examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their properties of multi-electron transfer depending on the number of ferrocene and TCBD moieties. Moreover, significant color changes were observed by visible spectroscopy under the electrochemical reduction conditions.
在[2+2]环加成反应中，通过多种炔烃与四氰基乙烯（TCNE）反应，随后使最初形成的[2+2]环加合物（即环丁烯衍生物）进行逆电环化反应，制备了在每个末端都带有一个二茂铁基的芳基取代的1,1,4,4-四氰基-1,3-丁二烯（FcTCBDs）和双（1,1,4,4-四氰基丁二烯）（双-FcTCBDs）。通过紫外/可见光谱研究了供体（二茂铁）和受体（TCBD）部分之间的特征性分子内电荷转移（ICT）。通过循环伏安法（CV）和差分脉冲伏安法（DPV）研究了FcTCBDs和双-FcTCBDs的氧化还原行为，结果表明它们具有取决于二茂铁和TCBD部分数量的多电子转移特性。此外，在电化学还原条件下通过可见光谱观察到了显著的颜色变化。
