Ultralong π-Conjugated Bis(terpyridine)metal Polymer Wires Covalently Bound to a Carbon Electrode: Fast Redox Conduction and Redox Diode Characteristics |
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| Authors: | Kuo-Hui Wu Ryota Sakamoto Hiroaki Maeda Eunice Jia Han Phua Hiroshi Nishihara |
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| Institution: | 1.Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan; (R.S.); (H.M.); (E.J.H.P.);2.Department of Chemistry, National Central University, 300 Jung-Da Rd. Jhong-Li 32001, Taiwan;3.Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan;4.Research Center for Science and Technology, Tokyo University of Science, Chiba 278-8510, Japan |
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| Abstract: | 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 (2-M, 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 (1-M) in a water–acetonitrile–HClO4 solution, affording ultralong wires up to 7400 mers (corresponding to ca. 15 μm). Both 2-Fe and 2-Ru 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/2-Fe]–2-Ru] (3) and GC/2-Ru]–2-Fe] (4), 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. |
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| Keywords: | electropolymerization coordination polymer electron transfer modified electrode redox hetero-metal complex diode |
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