Excited Organic Radicals in Photoredox Catalysis.

Abstract

Many important synthetic-oriented works have proposed excited organic radicals as photoactive species, yet mechanistic studies raised doubts about whether they can truly function as photocatalysts. This skepticism originates from the formation of (photo)redox-active degradation products and the picosecond decay of electronically excited radicals, which is considered too short for diffusion-based photoinduced electron transfer reactions. From this perspective, we analyze important synthetic transformations where organic radicals have been proposed as photocatalysts, comparing their theoretical maximum excited state potentials with the potentials required for the observed photocatalytic reactivity. We summarize mechanistic studies of structurally similar photocatalysts indicating different reaction pathways for some catalytic systems, addressing cases where the proposed radical photocatalysts exceed their theoretical maximum reactivity. Additionally, we perform a kinetic analysis to explain the photoinduced electron transfer observed in excited radicals on subpicosecond time scales. We further rationalize the potential anti-Kasha reactivity from higher excited states with femtosecond lifetimes, highlighting how future photocatalysis advancements could unlock new photochemical pathways.