Novel chemical pathways and charge-transport dynamics of electrodes modified with electropolymerized layers of [Co(v-terpy)2]2+

Abstract

Electropolymerized films of [Co(v-terpy)2]2+ (v-terpy is 4'-vinyl-2,2':6',2,'-terpyridinyl) exhibit reactivity patterns, especially with regard to ligand exchange, that differ significantly from those exhibited by [Co(terpy)2]2+ in solution. These differences are attributed to the physically constrained environment present in the polymer film. The charge-transport properties follow the model of Dahms and Ruff and the predicted concentration dependence of the diffusion coefficient. These electropolymerized films are also active in the electrocatalytic reduction of carbon dioxide.

Cobalt Polypyridyl Complexes as Redox Mediators for Lipoamide Dehydrogenase

“…As expected [29,34,35], they all exhibited two metal-centered redox processes, i.e., the Co 2þ/3þ and Co 2þ/þ oxidation and reduction processes, respectively (see Fig. 3a).…”

“…The complexes were synthesized following literature procedures [34,35]. Basically, the appropiate amount of Co(NO 3 ) 2 Á 6 H 2 O dissolved in water was mixed with a solution of the desired ligand in a metal to ligand molar ratio of 1:3 for the 1,10-phenanthroline (phen) and 2,2 0 -bipyridyl (bpy) ligands and 1:2 for 2,2 0 :6,2 00 -terpyridine (tpy).…”

Catalytic Applications of Terpyridines and their Transition Metal Complexes

“…Guadalupe et al. reported the electropolymerization155 of [Co(tpy‐vinyl) 2 ] 2+ onto glassy carbon electrodes and attributed the increased efficiency in the catalysis of the electroreduction of CO 2 to a more rigid environment within the polymer matrix and enhanced charge‐transport properties 20. However, a solvent dependence was observed, in which the electrode‐bound catalysts only showed high activity in polar weakly‐coordinating solvents (e.g.…”

“…Other important examples for the catalytic activity of Ru II monoterpyridine complexes are their ability to act as a reactive probe for the photoinduced cleavage of nucleic acids (photodynamic therapy, PDT), the CC bond formation by electrocatalytic reduction of CO 2 ,18 and the chemical water oxidation 19. For the same purpose, complexes of Co II and Rh III ions have also been reported 20. 21…”

Mechanistic study of the formation of multiblock π-conjugated metallopolymer

“…The surface coverage of the metallopolymer formed at 5 mV s -1 was 35.2 nmol cm -2 .The study of electronic conductivity can provide significant information about the charge-transport mechanism of poly[Ni(salophen)] produced by using the two electropolymerization scan rates studied (5 and 200 mV s -1 ). According to Abruña[26,27], the measurements of charge transport at chemically modified electrodes are related to physical movement of species, electron self-exchange, morphology of the deposited layer, and counterion transport. The conductivity profiles of poly[Ni(salophen)] shown inFig.3are also indicative of redox behavior.…”