Journal
MOLECULES
Volume 26, Issue 14, Pages -Publisher
MDPI
DOI: 10.3390/molecules26144267
Keywords
electropolymerization; coordination polymer; electron transfer; modified electrode; redox; hetero-metal complex; diode
Funding
- JST CREST [JPMJCR15F2]
- JSPS KAKENHI [JP19H05460]
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The study presents an efficient electrochemical method to synthesize pi-conjugated redox metal-complex linear polymer wires on glassy carbon surfaces, demonstrating fast redox conduction properties. The method allows for the creation of anisotropic hetero-metal-complex polymer wires with reversible redox reactions, showing potential for integrating functional molecules onto carbon surfaces.
We developed an efficient and convenient electrochemical method to synthesize pi-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 mu m). 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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