Using Lifetime and Quenching Rate Constant to Determine Optimal Quencher Concentration

A ABSTRACT Excited state quenching is a key step in photochemical reactions that involve energy or electron transfer. High reaction quantum yields require sufficiently high concentrations of a quencher to ensure efficient quenching. The determination of quencher concentrations is typically done through trial and error. Using kinetic modeling, however, a simple relationship was developed that predicts the concentration of quencher necessary to quench 90% of excited states, using only the photosensitizer lifetime and the rate constant for quenching as inputs. Comparison of the predicted quencher concentrations and quencher concentrations used in photoredox reactions featuring acridinium-based photocatalysts reveals that the majority of reactions used quencher concentrations significantly below the predicted concentration. This suggests that these reactions exhibit low quantum yields, requiring long reaction times and/or intense light sources.