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.
Keywords: copper catalysis; electrophotochemistry; luminescent copper; photoinduced homocoupling; photoredox catalysis.