This work implements a genetic algorithm (GA) to discover organic catalysts for photoredox CO2 reduction that are both highly active and resistant to degradation. The LUMO energy of the ground state catalyst is chosen as the activity descriptor and average Mulliken charge on all ring carbons as the descriptor for resistance to degradation via carboxylation (both obtained using density functional theory), to construct the fitness function of the GA. We combine the results of multiple GA runs, each based on different relative weighting of the two descriptors, and rigorously assess GA performance by calculating electron transfer barriers to CO2 reduction. A large majority of GA predictions exhibit improved performance relative to experimentally studied o-, m-, and p-terphenyl catalysts. Based on stringent cut-offs imposed on the average charge, barrier to electron transfer to CO2, and excitation energy, we recommend 25 catalysts for further experimental investigation of viability towards photoredox CO2 reduction.
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 CO 2 reduction and H 2 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 CO 2 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.
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