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Detailed photophysical investigation of a Mn(IV)-carbene complex has revealed that excitation into its lowest-energy absorption band (∼500 nm) results in the formation of an energetic ligand-to-metal charge-transfer (LMCT) state with a lifetime of 15 ns. To the best of our knowledge, this is the longest lifetime reported for charge-transfer states of first-row-based transition metal complexes in solution, barring those based on Cu, with a d