Thermally activated delayed fluorescence photocatalysts: a kinetic model to predict time-resolved spectroscopic experiments and photoreactions under continuous irradiation

PS excited states of TADF chromophores. Using analytical modeling and numerical simulations, we show that under pulsed excitation Stern-Volmer analysis is generally valid, unless very strong singlet-triplet coupling dominates and new analytical expressions are provided. Under continuous irradiation, quencher depletion leads to more complex kinetics described by quasi-steady-state treatments. Notably, triplet quenching is generally more productive than singlet quenching because of different cage escape yields, and our theoretical model predicts that the highest quenching efficiency does not necessarily yield the maximum photochemical quantum yield. These results highlight the need for rigorous kinetic modeling to optimize TADF-based photochemical reactions.