Solvent-dependent photochemical dynamics of a phenoxazine-based photoredox catalyst

Abstract

Abstract Organic substitutes for ruthenium and iridium complexes are increasingly finding applications in chemical syntheses involving photoredox catalysis. However, the performance of these organic compounds as electron-transfer photocatalysts depends on their accessible photochemical pathways and excited state lifetimes. Here, the UV-induced dynamics of N-phenyl phenoxazine, chosen as a prototypical N-aryl phenoxazine organic photoredox catalyst, are explored in three solvents, N,N-dimethyl formamide, dichloromethane and toluene, using ultrafast transient absorption spectroscopy. Quantum chemistry calculations reveal the locally excited or charge-transfer electronic character of the excited states, and are used to assign the transient electronic and vibrational bands observed. In toluene-d 8 , complete ground-state recovery is (31 ± 3) % by internal conversion (IC) from the photo-excited state (or from S 1 after IC but before complete vibrational relaxation), (13 ± 2) % via direct decay from vibrationally relaxed S 1 (most likely radiative decay, with an estimated radiative lifetime of 13 ns) and (56 ± 3) % via the T 1 state (with intersystem crossing (ISC) rate coefficient k ISC = (3.3 ± 0.2) × 10 8 s −1 ). In dichloromethane, we find evidence for excited state N-phenyl phenoxazine reaction with the solvent. Excited state lifetimes, ISC rates, and ground-state recovery show only modest variation with changes to the solvent environment because of the locally excited character of the S 1 and T 1 states.