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Updated: May 12, 2026

Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes
Published on: January 30, 2015
Coordination chemistry of single-site catalyst precursors in reductively electropolymerized vinylbipyridine films
Daniel P Harrison1, Alexander M Lapides, Robert A Binstead
1Department of Chemistry, Virginia Military Institute, Lexington, Virginia 24450, United States.
Abstract:
Reductive electropolymerization of [Ru(II)(PhTpy)(5,5'-dvbpy)(Cl)](PF6) and [Ru(II)(PhTpy)(5,5'-dvbpy)(MeCN)](PF6)2 (PhTpy is 4'-phenyl-2,2':6',2″-terpyridine; 5,5'-dvbpy is 5,5'-divinyl-2,2'-bipyridine) on glassy carbon electrodes gives well-defined films of poly{[Ru(II)(PhTpy)(5,5'-dvbpy)(Cl)](PF6)} (poly-1) or poly{[Ru(II)(PhTpy)(5,5'-dvbpy)(MeCN)](PF6)2} (poly-2). Oxidative cycling of poly-2 with added NO3(-) results in the replacement of coordinated MeCN by NO3(-) to give poly{[Ru(II)(PhTpy)(5,5'-dvbpy)(NO3)](+)}, and with 0.1 M HClO4, replacement by H2O occurs to give poly{[Ru(II)(PhTpy)(5,5'-dvbpy)(OH2)](2+)} (poly-OH2). Although analogous aqua complexes (e.g., [Ru(tpy)(bpy)(OH2)](2+)) undergo rapid loss of H2O to MeCN in solution, poly-OH2 and poly-OH2(+) are substitutionally inert in MeCN. The substitution chemistry is reversible, with reductive scans of poly-1 or poly-OH2 in MeCN resulting in poly-2, although with some loss of Faradaic response.
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