Proton-Coupled Electron Transfer between 4-Cyanophenol and Photoexcited Rhenium(I) Complexes with Different Protonatable Sites

Two rhenium­(I) tricarbonyl diimine complexes, one of them with a 2,2′-bipyrazine (bpz) and a pyridine (py) ligand in addition to the carbonyls ([Re­(bpz)­(CO)3(py)]+), and one tricarbonyl complex with a 2,2′-bipyridine (bpy) and a 1,4-pyrazine (pz) ligand ([Re­(bpy)­(CO)3(pz)]+) were synthesized, and their photochemistry with 4-cyanophenol in acetonitrile solution was explored. Metal-to-ligand charge transfer (MLCT) excitation occurs toward the protonatable bpz ligand in the [Re­(bpz)­(CO)3(py)]+ complex while in the [Re­(bpy)­(CO)3(pz)]+ complex the same type of excitation promotes an electron away from the protonatable pz ligand. This study aimed to explore how this difference in electronic excited-state structure affects the rates and the reaction mechanism for photoinduced proton-coupled electron transfer (PCET) between 4-cyanophenol and the two rhenium­(I) complexes. Transient absorption spectroscopy provides clear evidence for PCET reaction products, and significant H/D kinetic isotope effects are observed in some of the luminescence quenching experiments. Concerted proton–electron transfer is likely to play an important role in both cases, but a reaction sequence of proton transfer and electron transfer steps cannot be fully excluded for the 4-cyanophenol/[Re­(bpz)­(CO)3(py)]+ reaction couple. Interestingly, the rate constants for bimolecular excited-state quenching are on the same order of magnitude for both rhenium­(I) complexes.