Synthesis, crystal structure, photophysical properties and theoretical studies of [Cu3(Ph2PCH2PPh2)3(WS4)]ClO4
Abstract
The reaction of [Cu2(dppm)2(MeCN)4]2+[dppm = bis(diphenylphosphino)methane] with [WS4]2– gives the cationic d0-d10 complex [Cu3(dppm)3(WS4)]+, the crystal structure of which has been determined. The three copper atoms and the thiotungstate ligand form a distorted ‘flywheel’ array with W ⋯ Cu separations of 2.790(3), 2.803(3) and 2.834(3)Å. In the solid state the complex shows an intense emission with λmax at 615 nm. Extended-Hückel molecular-orbital calculations reveal that the emitting state may arise from a [ψ(Cu,P)→ WVI] charge-transfer transition.