title: Unveiling the structure of polytetraruthenated nickel porphyrin by Raman spectroelectrochemistry.
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.
authors: †Instituto de Química, Universidade de São Paulo, CEP 05508-000 Sao Paulo, SP, Brazil.
authors: Luís M C
authors: LM
authors: Ferreira
authors: †Instituto de Química, Universidade de São Paulo, CEP 05508-000 Sao Paulo, SP, Brazil.
authors: Daniel
authors: D
authors: Grasseschi
authors: †Instituto de Química, Universidade de São Paulo, CEP 05508-000 Sao Paulo, SP, Brazil.
authors: Mauro S F
authors: MS
authors: Santos
authors: ‡Instituto de Química, Universidade Federal de Goiás, CEP 74001970 Goiania, GO, Brazil.
authors: Paulo R
authors: PR
authors: Martins
authors: †Instituto de Química, Universidade de São Paulo, CEP 05508-000 Sao Paulo, SP, Brazil.
authors: Ivano G R
authors: IG
authors: Gutz
authors: †Instituto de Química, Universidade de São Paulo, CEP 05508-000 Sao Paulo, SP, Brazil.
authors: Ana Maria C
authors: AM
authors: Ferreira
authors: †Instituto de Química, Universidade de São Paulo, CEP 05508-000 Sao Paulo, SP, Brazil.
authors: Koiti
authors: K
authors: Araki
authors: †Instituto de Química, Universidade de São Paulo, CEP 05508-000 Sao Paulo, SP, Brazil.
authors: Henrique E
authors: HE
authors: Toma
authors: †Instituto de Química, Universidade de São Paulo, CEP 05508-000 Sao Paulo, SP, Brazil.
authors: Lúcio
authors: L
authors: Angnes