Role of Cobalt(III) Cationic Complexes in the Self-Assembling Process of a Water Soluble Porphyrin

Under moderate acidic conditions, the cationic (+3) complexes ions tris(1,10-phenanthroline)cobalt(III), [Co(phen)₃]³⁺, and hexamminecobalt(III), [Co(NH₃)₆]³⁺, efficiently promote the self-assembling process of the diacid 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (H₂TPPS₄) into J-aggregates. The growth kinetics have been analyzed according to a well-established autocatalytic model, in which the rate determining step is the initial formation of a nucleus containing m porphyrin units (in the range 2-3), followed by a stage whose rate constant k evolves as a power of time. The observed catalytic rate constants and the extent of J-aggregation increase on increasing the metal complex concentration, with the phen complex being the less active. The UV/Vis extinction spectra display quite broad envelops at the J-band, especially for the amino-complex, suggesting that electronic dipolar coupling between chromophores is operative in these species. The occurrence of spontaneous symmetry breaking has been revealed by circular dichroism and the measured dissymmetry g-factor decreases on increasing the aggregation rates. The role of these metal complexes on the growth and stabilization of porphyrin nano-assemblies is discussed in terms of the different degree of hydrophilicity and hydrogen bonding ability of the ligands present in the coordination sphere around the metal center.