Calculations of the ET and PCET rates. The Marcus theory was used to calculate the ET rates (Eq. 1). Herein, ∆G° is the reaction free energy based on the QM calculations. Vel is the electronic coupling calculated using the fragment charge difference (FCD) method implemented in the Qchem program and by considering the distance correction. 𝜆 is the total reorganization energy, in which the innersphere reorganization energy was calculated by using the four-point method, while outer-sphere (or solvent) reorganization energy was calculated by the two-sphere model.