Fluorescence quenching of photoreaction products in the excited singlet state

Abstract

The properties of steady-state spontaneous luminescence of a quantum system with a photoproduct with recordable fluorescence under the conditions of dynamic quenching of excited states by extraneous substances were considered. It was shown that the dependence of photoproduct fluorescence intensity and yield on quencher concentration was nontrivial and could not be conveniently used to determine the Stern-Volmer constant. At the same time, the initial form of the luminophore and its photoproduct produced in a kinetically controlled reaction are quenched in such a way that the ratio of their fluorescence intensities increases linearly as the quencher concentration grows. The corresponding equation was used to determine the constant of bimolecular quenching of reaction product excited states. The results were used in an analysis of the experimental fluorescence spectra of flavone (3-hydroxiflavone), whose fluorescence was excited under the conditions of dynamic quenching of the S1 state. Our analysis was shown to be applicable to a wide range of compounds with photoreactions accompanied by two-band fluorescence (charge transfer, proton transfer, phosphorescence, complex formation, etc.). It could be used to accurately determine bimolecular contact constants for excited states of photoreaction product molecules.