Aggregation of zinc tetraphenylporphyrin characterized by ensemble and single-molecule fluorescence spectroscopy

The aggregation of metalloporphyrins is believed to play a crucial role in the excited-state annihilation process known as triplet–triplet annihilation, which in turn has significant potential applications in photon upconversion schemes. In this work, the propensity of the water-soluble metalloporphyrin zinc (II) meso-tetra(4-sulfonatophenyl)porphine to undergo aggregation when adsorbed to glass cover slips was investigated by single-molecule fluorescence microscopy. In proof-of-principle experiments, it was demonstrated (1) that individual molecules of the metalloporphyrin can be directly visualized in spite of their very weak fluorescence emission, and (2) that at low concentrations (10−8 mol/L), the molecule has a strong tendency to form multimolecular aggregates. A subset of the multimolecular aggregates shows a significant blue-shift in fluorescence emission, though at present the precise nature of the molecular aggregates remains unclear.