Wu Kuo-Hui, Sakamoto Ryota, Maeda Hiroaki, Phua Eunice Jia Han, Nishihara Hiroshi
Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Department of Chemistry, National Central University, 300 Jung-Da Rd. Jhong-Li 32001, Taiwan.
Molecules. 2021 Jul 14;26(14):4267. doi: 10.3390/molecules26144267.
We developed an efficient and convenient electrochemical method to synthesize π-conjugated redox metal-complex linear polymer wires composed of azobenzene-bridged bis(terpyridine)metal (, M = Fe, Ru) units covalently immobilized on glassy carbon (GC). Polymerization proceeds by electrochemical oxidation of bis(4'-(4-anilino)-2,2':6',2″-terpyridine)metal () in a water-acetonitrile-HClO solution, affording ultralong wires up to 7400 mers (corresponding to ca. 15 μm). Both and undergo reversible redox reactions, and their redox behaviors indicate remarkably fast redox conduction. Anisotropic hetero-metal-complex polymer wires with Fe and Ru centers are constructed via stepwise electropolymerization. The cyclic voltammograms of two hetero-metal-complex polymer wires, GC/[]-[] () and GC/[]-[] (), show irreversible redox reactions with opposite electron transfer characteristics, indicating redox diodelike behavior. In short, the present electrochemical method is useful to synthesize polymer wire arrays and to integrate functional molecules on carbon.
我们开发了一种高效便捷的电化学方法，用于合成由偶氮苯桥联双（三联吡啶）金属（，M = Fe，Ru）单元共价固定在玻碳（GC）上组成的π共轭氧化还原金属络合物线性聚合物线。聚合反应通过双（4'-（4-苯胺基）-2,2':6',2″-三联吡啶）金属（）在水-乙腈-HClO溶液中的电化学氧化进行，得到长达7400个单体（约15μm）的超长导线。 和 都经历可逆的氧化还原反应，并且它们的氧化还原行为表明氧化还原传导非常快。通过逐步电聚合构建了具有Fe和Ru中心的各向异性异金属络合物聚合物线。两根异金属络合物聚合物线GC/[]-[]（）和GC/[]-[]（）的循环伏安图显示出具有相反电子转移特性的不可逆氧化还原反应，表明具有氧化还原二极管样行为。简而言之，目前的电化学方法可用于合成聚合物线阵列并将功能分子整合到碳上。
