Supramolecular assemblies of phenolic metalloporphyrins: Structures and electrochemical studies

The reactivity of two phenolic porphyrins bearing respectively catechol and gallol-derived meso substituents (5,10,15,20-tetrakis(3,4-dihydroxyphenyl)porphyrin and 5,10,15,20-tetrakis(3,4,5-trihydroxyphenyl)porphyrin) with trivalent metallic ions (Fe, Mn, In) was studied. Six supramolecular compounds were obtained and structurally characterized by single crystal X-ray diffraction. In each compound, the supramolecular assembly was based on the axial coordination of a phenolate function to the metallic ion lying in the porphyrinic core. A great diversity of supramolecular architectures was accessible through such simple arrangements, and objects ranging from dimers to one-dimensional polymers were isolated. Some of these assemblies were further investigated in solution by mass spectrometry and by UV-vis absorption spectroscopy. For the iron-based materials, the redox behavior was studied in solution through cyclic voltammetry experiments in inert conditions and under air.