Unveiling the Structure of Polytetraruthenated Nickel Porphyrin by Raman Spectroelectrochemistry

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Abstract
The structure of polytetraruthenated nickel porphyrin was unveiled for the first time by electrochemistry, Raman spectroelectrochemistry, and a hydroxyl radical trapping assay. The electrocatalytic active material, precipitated on the electrode surface after successive cycling of [NiTPyP{Ru(bipy)2Cl}4]4+ species in strong aqueous alkaline solution (pH 13), was found to be a peroxo-bridged coordination polymer. The electropolymerization process involves hydroxyl radicals (as confirmed by the characteristic set of DMPO/•OH adduct EPR peaks) as reaction intermediates, electrocatalytically generated in the 0.80–1.10 V range, that induce the formation of Ni–O–O–Ni coordination polymers, as evidenced by Raman spectroelectrochemistry and molecular modeling studies. The film growth is halted above 1.10 V due to the formation of oxygen gas bubbles.
Funding Information
  • Fundação de Amparo à Pesquisa do Estado de São Paulo (2011/00037-6)
  • Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
  • Conselho Nacional de Desenvolvimento Científico e Tecnológico

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