Chemistry

[ASAP] Light-Driven Proton-Coupled Two-Electron Ligand Reduction Causes the Rearrangement of the Coordination Sphere in Cu(I) 4H-Imidazolato Complexes

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This study investigates copper(I) complexes bearing 4H-imidazolato ligands and demonstrates that light irradiation triggers a proton-coupled two-electron reduction of the ligand, leading to a structural reorganization of the coordination sphere around the copper center. The photochemical process involves the uptake of protons alongside the two-electron reduction event, which drives the geometric rearrangement rather than simple redox changes at the metal. These findings reveal that the ligand itself acts as the primary site of photoreactivity, rather than the copper ion, distinguishing this system from classical metal-centered photochemistry.


Understanding light-driven proton-coupled electron transfer in copper complexes has direct relevance to the design of earth-abundant metal catalysts for solar energy conversion and artificial photosynthesis. Copper-based systems offer a cost-effective alternative to precious metal catalysts, and insights into their photochemical behavior can guide the development of more efficient light-driven catalytic cycles.


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Journal of the American Chemical Society
DOI: 10.1021/jacs.6c00920

Source: [ASAP] Light-Driven Proton-Coupled Two-Electron Ligand Reduction Causes the Rearrangement of the Coordination Sphere in Cu(I) 4H-Imidazolato Complexes