Exploiting Charge-Transfer States for Maximizing Intersystem Crossing Yields in Organic Photoredox Catalysts

A key feature of prominent transition-metal-containing photoredox catalysts (PCs) is high quantum yield access to long-lived excited states characterized by a change in spin multiplicity. For organic PCs, challenges emerge for promoting excited-state intersystem crossing (ISC), particularly when potent excited-state reductants are desired. Herein, we report a design exploiting orthogonal π-systems and an intermediate-energy charge-transfer excited state to maximize ISC yields (Φ ISC ) in a highly reducing ( E 0 * = −1.7 V vs SCE), visible-light-absorbing phenoxazine-based PC. Simple substitution of N -phenyl for N -naphthyl is shown to dramatically increase Φ ISC from 0.11 to 0.91 without altering catalytically important properties, such as E 0 *.