Spectroscopic and kinetic investigations on porphyrin J-aggregates induced by polyamines

A non-covalent supramolecular approach to build up mesoscopic fractal J-aggregates of meso-tetrakis(4- sulfonatophenyl)porphyrin by using different polyamines under mild acidic conditions is reported. Spermine-induced J-aggregates have been treated as a model system for a kinetic investigation. The kinetic analysis has been performed through two non-conventional approaches as function of a different reagent mixing protocol. In particular, an autocatalytic pathway in which the formation of aggregation nuclei is the rate-determining step is found when porphyrin is added to the reaction mixture as first reagent. In order to gain information on this early stage, a kinetic investigation has been carried out as function of different parameters, such as pH, and both spermine and porphyrin concentration. The nucleation becomes particularly evident when polyamines with fewer than three protonable nitrogen atoms are used. In these cases, a sort of "YES/NO" effect for the aggregation process has been found as a function of the reagent mixing order protocol. Most importantly, the observed kinetic behavior strongly affects the mesoscopic structure of the final aggregates.