Four new heteroleptic Cu(I) complexes based on 1, 2, 3‐triazolyl‐quinoline or quinoxaline and a chelating diphosphine were prepared and fully characterised. The mononuclear derivatives absorb in the visible region, up to 600 nm, while the dinuclear complex has a long‐tail absorption up to 800 nm, showing an additional electronic state corroborated by theoretical calculations. Although a methylene group between the triazole and the quino(xa)line moiety increases the bite angle and decreases the luminescence in solution, all complexes emit brightly in the solid‐state. Their redox properties in the excited state were determined, proving their ability in serving as photoredox catalysts in atom transfer radical addition successfully.
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