Abstract
Organic photocatalysis has been developed flourishingly to rely on bimolecular energy transfer (EnT) or oxidative/reductive electron transfer (ET), promoting a variety of synthetic transformations. However, there are rare examples to merge EnT and ET processes rationally within one chemical system, of which the mechanistic investigation still remains in its infancy. Herein, the first mechanistic illustration and kinetic assessments of the dynamically associated EnT and ET paths were conducted for realizing the C-H functionalization in a cascade photochemical transformation of isomerization and cyclization by using the dual-functional organic photocatalyst of riboflavin. An extended single-electron transfer model of transition-state-coupled dual-nonadiabatic crossings was explored to analyze the dynamic behaviors in the proton transfer-coupled cyclization. This can also be used to clarify the dynamic correlation with the EnT-driven E → Z photoisomerization that has been kinetically evaluated by using Fermi's golden rule with the Dexter model. The present computational results of electron structures and kinetic data contribute to a fundamental basis for understanding the photocatalytic mechanism of the combined operation of EnT and ET strategies, which will guide the design and manipulation for the implementation of multiple activation modes based on a single photosensitizer.