Mechanism of a Luminescent Dicopper System That Facilitates Electrophotochemical Coupling of Benzyl Chlorides via a Strongly Reducing Excited State

Photochemical radical generation has become a modern staple in chemical synthesis and methodology. Herein, we detail the photochemistry of a highly reducing, highly luminescent dicopper system [Cu2] (Eox* ≈ −2.7 V vs SCE; τ0 ≈ 10 μs) within the context of a model reaction: single-electron reduction of benzyl chlorides. The dicopper system is mechanistically well defined. As we show, it is the [Cu2]* excited state that serves as the outer-sphere photoreductant of benzyl chloride substrates; the ground-state oxidized byproduct, [Cu2]+, is electrochemically recycled, demonstrating a catalytic electrophotochemical C–C coupling process.