Co(III)-tetra(4-sulfonatophenyl)porphyrin complexes with bidentate ligands in aqueous buffer media

Abstract

The processes of hydrophilic Co(III)-tetra(4-sulfonatophenyl)porphyrin supramolecular assembly with 4,4-bipyridyl in aqueous buffer media have been studied by UV-vis, 1D and 2D 1H NMR-spectroscopy. In the case of 1,4-diazabicyclo[2.2.2]octane, pyrazine and piperazine in aqueous solutions, no assembly was observed. Interactions of the hydrophilic Co(III)-tetraarylporphyrin with ionic micelles (cationic surfactants with different alkyl tail lengths) in buffer media were investigated. These studies were performed by the UV-vis, 1D NOESY-spectroscopy and dynamic lightscattering (DLS) methods. The metalloporphyrins were incorporated into the hydrophobic part of micelles, which led to Co(III) reduction to Co(II) in the Co-porphyrinate composition. The rate of Co(III) reduction accompanied by detachment of additional ligands coordinated on Co(III)-porphyrins or disruption of supramolecular dimers and depends on the surfactant concentration and nature. The results obtained indicate the possibility of creating supramolecular porphyrin-based assemblies with the preprogrammed lifetime (from several hours to several days) and could be used in the creation of host-guest systems for recognition, selective binding and the prolonged release of bioactive substrates as the means in the designing of biomimetic systems with effective binding affinities to heterocycles, DNA base pairs and RNA.