Shoji Taku, Ito Shunji
Department of Material Science, Graduate School of Science and Technology, Shinshu University, Matsumoto, 390-8621, Nagano, Japan.
Graduate School of Science and Technology, Hirosaki University, Hirosaki, 036-8561, Aomori, Japan.
Chemistry. 2017 Nov 27;23(66):16696-16709. doi: 10.1002/chem.201702806. Epub 2017 Oct 24.
We describe the synthesis and properties of azulene-substituted 1,1,4,4-tetracyanobutadienes (AzTCBDs) and heteroazulenyl TCBDs. TCBD derivatives were prepared in good to excellent yields through reaction of the corresponding 1-ethynylazulenes with tetracyanoethylene (TCNE). In contrast, the reaction between propargyl alcohols and the 1-azulenyl group in TCNE generated 2-aminofuran derivatives, which were transformed into 6-aminofulvenes with a 1-azulenyl substituent upon treatment with several amines. The optical and electrochemical properties of the AzTCBDs were clarified by UV/Vis and voltammetry. The AzTCBD derivatives exhibited electrochromism, showing a multi-step color change under electrochemical redox conditions. The multistage redox properties of AzTCBDs could be useful for the development of novel organic electronic materials.
我们描述了薁取代的1,1,4,4-四氰基丁二烯（AzTCBDs）和杂薁基TCBDs的合成及性质。通过相应的1-乙炔基薁与四氰基乙烯（TCNE）反应，以良好至优异的产率制备了TCBD衍生物。相比之下，炔丙醇与TCNE中的1-薁基之间的反应生成了2-氨基呋喃衍生物，在用几种胺处理后，这些衍生物转化为带有1-薁基取代基的6-氨基富烯。通过紫外/可见光谱和伏安法阐明了AzTCBDs的光学和电化学性质。AzTCBD衍生物表现出电致变色现象，在电化学氧化还原条件下呈现多步颜色变化。AzTCBDs的多级氧化还原性质可能有助于新型有机电子材料的开发。
