Photoredox Chemistry with Organic Catalysts: Role of Computational Methods

Organic catalysts have the potential to carry out a wide range of otherwise thermally inaccessible reactions via photoredox routes. Early demonstrated successes of organic photoredox catalysts include one-electron CO₂ reduction and H₂ generation via water splitting. Photoredox systems are challenging to study and design owing to the sheer number and diversity of phenomena involved, including light absorption, emission, intersystem crossing, partial or complete charge transfer, and bond breaking or formation. Designing a viable photoredox route therefore requires consideration of a host of factors such as absorption wavelength, solvent, choice of electron donor or acceptor, and so on. Quantum chemistry methods can play a critical role in demystifying photoredox phenomena. Using one-electron CO₂ reduction with phenylene-based chromophores as an illustrative example, this perspective highlights recent developments in quantum chemistry that can advance our understanding of photoredox processes and proposes a way forward for driving the design and discovery of organic catalysts.