Potent Bis-Cyclometalated Iridium Photoreductants with β-Diketiminate Ancillary Ligands

In this work, we outline a strategy to prepare a class of improved visible-light photosensitizers. Bis-cyclometalated iridium complexes with electron-rich β-diketiminate (NacNac) ancillary ligands are demonstrated to be potent excited-state electron donors. Evaluation of the photophysical and electrochemical properties establishes the excited-state redox potentials of the complexes, and Stern-Volmer quenching experiments inform on the kinetics of photoinduced electron transfer to the model substrates methyl viologen (MV²⁺) and benzophenone (BP). Compared to fac-Ir(ppy)₃ (ppy = 2-phenylpyridine), widely regarded as a state-of-the-art photoreductant, the complexes we describe have excited-state redox potentials that are more potent by 300-400 mV and rates for photoinduced electron transfer that are accelerated by as much as a factor of 3. These complexes emerge as promising targets for application in photocatalytic reactions and other photochemical processes.