Characterizing pyrene–Ag+ exciplex formation in aqueous and ethanolic solutions

The primary mechanism responsible for the dynamic fluorescence quenching of polycyclic aromatic compounds (PACs) by Ag+ ions is enhanced intersystem crossing from the lowest singlet excited state to the lowest triplet excited state. For some PACs, however, exciplex formation with Ag+ in polar organic solvents has also been reported. Quenching of pyrene fluorescence by Ag+ in two polar solvent systems (aqueous and ethanolic solutions) was examined here using steady-state and time-resolved fluorescence techniques. In both solvents, quenching led to the formation of a pyrene–Ag+ exciplex, <F>(1Py⋯Ag+)*</F>, which rapidly equilibrated with excited singlet pyrene molecules (<F>1Py*</F>) and Ag+ ions. The exciplex and pyrene monomer emission spectra strongly overlapped, with the dominant exciplex peaks in water and ethanol red shifted from the 0–0 transition of pyrene by 5.08 and 2.56 kJ/mol, respectively. Rate constants for the formation and dissociation of the exciplex were much larger than the radiative and nonradiative decay rate constants for both the excited state monomer and exciplex. The short exciplex fluorescence lifetimes and very low quantum yields observed in the two solvents can be attributed to enhanced nonradiative decay processes for the exciplex. The emission quantum yield of the exciplex formed in aqueous solution was approximately an order of magnitude larger than that in ethanolic solution, which is likely to be attributable to the higher polarity of water versus ethanol. [Copyright &y& Elsevier]