Oxidative two-state photoreactivity of a manganese(IV) complex using near-infrared light

Highly reducing or oxidizing photocatalysts are a fundamental challenge in photochemistry. Only a few transition metal complexes with Earth-abundant metal ions have so far advanced to excited state oxidants. All these photocatalysts require high-energy light for excitation, and their oxidizing power has not been fully exploited due to energy dissipation before reaching the photoactive state. Here we demonstrate that the complex [Mn(dgpy) 2 ] 4+ , based on Earth-abundant manganese and the tridentate 2,6-diguanidylpyridine ligand (dgpy), evolves to a luminescent doublet ligand-to-metal charge transfer ( 2 LMCT) excited state (1,435 nm, 0.86 eV) with a lifetime of 1.6 ns after excitation with low-energy near-infrared light. This 2 LMCT state oxidizes naphthalene to its radical cation. Substrates with extremely high oxidation potentials up to 2.4 V enable the [Mn(dgpy) 2 ] 4+ photoreduction via a high-energy quartet 4 LMCT excited state with a lifetime of 0.78 ps, proceeding via static quenching by the solvent. This process minimizes free energy losses and harnesses the full photooxidizing power, and thus allows oxidation of nitriles and benzene using Earth-abundant elements and low-energy light. The design of highly oxidizing Earth-abundant transition metal complexes for photochemical applications is desirable, but progress in this area remains limited. Now a manganese(IV) diguanidylpyridine complex has been shown to photooxidize naphthalene, benzene and acetonitrile to their radical cations after excitation with near-infrared light. Experimental and theoretical studies indicate the presence of two distinct ligand-to-metal charge transfer excited states.