Supramolecular Conformational Effects in the Electrocatalytic Properties of Electrostatic Assembled Films of Meso(3- and 4-Pyridyl) Isomers of Tetraruthenated Porphyrins

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 phthalocyanin...

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Bibliographic Details
Published in:Journal of the Mexican Chemical Society 2005, Vol.49 (2), p.180-187
Main Authors: Mayer, Ildemar, Eberlin, Marcos N., Tomazela, Daniela M., Toma, Henrique E., Araki, Koiti
Format: Article
Language:Portuguese
Subjects:
Chemistry, Multidisciplinary
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Summary: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.
ISSN:1870-249X