Environmentally Friendly Mechanochemical Syntheses and Conversions of Highly Luminescent Cu(I) Dinuclear Complexes.

Luminescent dinuclear Cu(I) complexes, [Cu2X2(dpypp)2] [Cu-X; X = Cl, Br, I; dpypp = 2,2'-(phenylphosphinediyl)dipyridine], were successfully synthesized by a solvent-assisted mechanochemical method. A trace amount of the assisting solvent plays a key role in the mechanochemical synthesis; only two solvents possessing the nitrile group, CH3CN and PhCN, were effective for promoting the formation of dinuclear Cu-X. X-ray analysis revealed that the dinuclear structure with no Cu···Cu interactions, bridged by two dpypp ligands, was commonly formed in all Cu-X species. These complexes exhibited bright green emission in the solid state at room temperature (Φ = 0.23, 0.50, and 0.74; λem = 528, 518, and 530 nm for Cu-Cl, Cu-Br, and Cu-I, respectively). Emission decay measurement and TD-DFT calculation suggested that the luminescence of Cu-X could be assigned to phosphorescence from the triplet metal-to-ligand charge-transfer ((3)MLCT) excited state, effectively mixed with the halide-to-ligand charge-transfer ((3)XLCT) excited state, at 77 K. The source of emission changed to thermally activated delayed fluorescence (TADF) with the same electronic transition nature at room temperature. In addition, the CH3CN-bound analogue, Cu2(CH3CN)2(dpypp)22, was successfully mechanochemically converted to Cu-X by grinding with solid KX in the presence of a trace amount of assisting water.