Ildemar Mayer

Supramolecular conformational effects in the electrocatalytic properties of electrostatic assembled films of meso(3- and 4-pyridyl) isomers of tetraruthenated porphyrins

, 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.

Spectroelectrochemical behavior of N-confused dioxohexaphyrins

Doubly N-confused dioxohexaphyrins were characterized by cyclic voltammetry and spectroelectrochemistry in the -2.5 to +2.0 V vsAg|Ag+ (0.10 M, in CH3CN) range. Six reversible monoelectronic processes were found suggesting that the rich electrochemistry of porphyrin systems was preserved in that expanded macrocycle. However, the electronic and electrochemical properties of the free-base, Cu(II) and Ni(II) species were shown to be sensitive to the coordinated transition metal ions and solvent revealing a quite complex behavior, probably reflecting the higher flexibility and strong conformational effects on the energy levels and stability of those complexes.

Electronic conduction and electrocatalysis by supramolecular tetraruthenated copper porphyrazine films

A new tetraruthenated copper(II)-tetra(3,4-pyridyl)porphyrazine species, [CuTRPyPz]4+, has been synthesized and fully characterized by means of analytical, spectroscopic and electrochemical techniques. This A-conjugated system contrasts with the related meso-tetrapyridylporphyrins by exhibiting strong electronic interaction between the coordinated peripheral complexes and the central ring. Based on favorable A-stacking and electrostatic interactions, layer-by-layer assembled films were successfully generated from the appropriate combination of [CuTRPyPz]4+ with copper(II)-tetrasulfonated phtalocyanine, [CuTSPc]4-. Their conducting and electrocatalytic properties were investigated by means of impedance spectroscopy and rotating disc voltammetry, exhibiting metallic behavior near the Ru(III/II) redox potential, as well as enhanced catalytic activity for the oxidation of nitrite and sulphite ions.