Resumen

MAYER, Ildemar et al. Supramolecular Conformational Effects in the Electrocatalytic Properties of Electrostatic Assembled Films of Meso(3- and 4-Pyridyl) Isomers of Tetraruthenated Porphyrins. J. Mex. Chem. Soc [online]. 2005, vol.49, n.2, pp.180-187. ISSN 1870-249X.

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.

Palabras llave : supramolecular chemistry; metalloporphyrins; electrostatic assembled films; electrocatalysis; electrochemistry; mass spectrometry.