Exploiting Potential Inversion for Photoinduced Multielectron Transfer and Accumulation of Redox Equivalents in a Molecular Heptad

Photoinduced multielectron transfer and reversible accumulation of redox equivalents is accomplished in a fully integrated molecular heptad composed of four donors, two photosensitizers, and one acceptor. The second reduction of the dibenzo­[1,2]­dithiin acceptor occurs more easily than the first by 1.3 V, and this potential inversion facilitates the light-driven formation of a two-electron reduced state with a lifetime of 66 ns in deaerated CH₃CN. The quantum yield for formation of this doubly charge-separated photoproduct is 0.5%. In acidic oxygen-free solution, the reduction product is a stable dithiol. Under steady-state photoirradiation, our heptad catalyzes the two-electron reduction of an aliphatic disulfide via thiolate-disulfide interchange. Exploitation of potential inversion for the reversible light-driven accumulation of redox equivalents in artificial systems is unprecedented and the use of such a charge-accumulated state for multielectron photoredox catalysis represents an important proof-of-concept.