Please use this identifier to cite or link to this item: http://repositorio.unicamp.br/jspui/handle/REPOSIP/25207
Type: Artigo de periódico
Title: Supramolecular conformational effects in the electrocatalytic properties of electrostatic assembled films of meso(3- and 4-pyridyl) isomers of tetraruthenated porphyrins
Author: Mayer, Ildemar
Eberlin, Marcos N.
Tomazela, Daniela M.
Toma, Henrique E.
Araki, Koiti
Abstract: Meso(3- and 4-pyridyl)porphyrins coordinated to four [Ru(bipy)2Cl]+ complexes, M(3-TRPyP) or M(4-TRPyP), where M=2H+ and Zn2+, have been obtained and characterized by electrochemistry, spectroscopy and mass spectrometry. Layer-by-layer electrostatic assembled films with tetrasulfonated phthalocyaninatecuprate(II) anion, CuTSPc, displayed distinct electrocatalytic activity towards sulfite and nitrite oxidation. In general, the films derived from the M(4-TRPyP) isomers are more effective for the oxidation of nitrite, whereas those containing the M(3-TRPyP) isomers are more efficient for the oxidation of sulfite. The results demonstrated the influence of molecular geometry on the active sites of porphyrinic nanomaterials, enhancing the electron-transfer process in the M(3-TRPyP) derivative. This effect results from changes in the chemical environment around the active sites, induced by the contrasting molecular packing interactions with CuTSPc.
Meso (3- e 4-piridil)porfirinas coordenadas a quatro complexos [Ru(bipy)2Cl]+, M(3-TRPyP) e M(4-TRPyP), onde M = 2H+ e Zn2+, foram obtidas e caracterizadas por métodos eletroquímicos, espectroscopia e espectrometria de massas. Os filmes eletrostaticamente montados camada por camada com ftalocianina de cobre tetrassulfonada, CuTSPc, apresentaram atividade eletrocatalítica diferenciada para a oxidação de sulfito e nitrito. Em geral, os filmes derivados dos isômeros M(4-TRPyP) são mais ativos para a oxidação de nitrito, enquanto aqueles contendo os isômeros M(3-TRPyP) são mais eficientes para a oxidação de sulfito. Os resultados revelaram uma influência significativa da geometria molecular no sítio ativo dos nanomateriais porfirínicos, que favorece os processos de transferência eletrônica nos derivados de M(3-TRPyP), através de mudanças no empacotamento molecular com a CuTSPc.
Subject: supramolecular chemistry
metalloporphyrins
electrostatic assembled films
electrocatalysis
electrochemistry
mass spectrometry
Editor: Sociedade Brasileira de Química
Rights: aberto
Identifier DOI: 10.1590/S0103-50532005000300016
Address: http://dx.doi.org/10.1590/S0103-50532005000300016
http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532005000300016
Date Issue: 1-Jun-2005
Appears in Collections:Artigos e Materiais de Revistas Científicas - Unicamp

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