Computational Analysis of Electron Transfer Kinetics for CO2 Reduction with Organic Photoredox Catalysts

We present a fundamental description of the electron transfer (ET) step from substituted oligo(p-phenylene) (OPP) radical anions to CO2, with the larger goal of assessing the viability of underexplored, organic photoredox routes for utilization of anthropogenic CO2. This work varies the electrophilicity of para-substituents to OPP and probes the dependence of rate coefficients and interfragment interactions on the substituent Hammett parameter, sigma(p), using constrained density functional theory (CDFT) and energy decomposition analysis (EDA). Large electronic couplings across substituents indicates an adiabatic electron transfer process for reactants at contact. As one might intuitively expect, free energy changes dominate trends in ET rate coefficients in most cases, and rates increase with substituent electron-donating ability. However, we observe an unexpected dip in rate coefficients for the most electron-donating groups, due to the combined impact of flattening free energies and a steep increase in reorganization energies. Our analysis shows that, with decreasing sigma(p), flattening OPP LUMO levels lower the marginal increase in free energy. EDA reveals trends in electrostatics and charge transfer interactions between the catalyst and substrate fragments that influence free energy changes across substituents. Reorganization energies do not exhibit a direct dependence on sigma(p) and are largely similar across systems, with the exception of substituents containing lone pairs of electrons that exhibit significant deformation upon electron transfer. Our study therefore suggests that while a wide range of ET rates are observed, there is an upper limit to rate enhancements achievable by only tuning the substituent electrophilicity.