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(c) 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.

Automated summary

Under moderate acidic conditions, cobalt complexes ions play an efficient role in promoting the self-assembling process of porphyrin molecules into J-aggregates, with the amino complex being more active than the phen complex. Growth kinetics analysis reveals the existence of nucleus formation and evolving rate constants during the aggregation process.