Photoexcitation and One-Electron Reduction Processes of a CO2Photoreduction Dyad Catalyst Having a Zinc(II) Porphyrin Photosensitizer

We have explored the photophysical properties and one-electron reduction process in the dyad photocatalyst for CO2photoreduction, ZnP-phen=Re, in which the catalyst of fac-[Re(1,10-phenanthoroline)(CO)3Br] is directly connected with the photosensitizer of zinc(II) porphyrin (ZnP), using time-resolved infrared spectroscopy, transient absorption spectroscopy, and quantum chemical calculations. We revealed the following photophysical properties: (1) the intersystem crossing occurs with a time constant of ∼20 ps, which is much faster than that of a ZnPsingle unit, and (2) the charge density in the excited singlet and triplet states is mainly localized on ZnP, which means that the excited state is assignable to the π–π* transition in ZnP. The one-electron reduction by 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole occurs via the triplet excited state with the time constant of ∼100 ns and directly from the ground state with the time constant of ∼3 μs. The charge in the one-electron reduction species spans ZnPand the phenanthroline ligand, and the dihedral angle between ZnPand the phenanthroline ligand is rotated by ∼24° with respect to that in the ground state, which presumably offers an advantage for proceeding to the next CO2reduction process. These insights could guide the new design of dyad photocatalysts with porphyrin photosensitizers.