Syntheses, Photophysics, and Photochemistry of Trinuclear Copper(I) Thiolate and Hexanuclear Copper(I) Selenolate Complexes: X-ray Crystal Structures of [Cu<sub>6</sub>(μ-dppm)<sub>4</sub>(μ<sub>3</sub>-SePh)<sub>4</sub>](BF<sub>4</sub>)<sub>2</sub> and [Cu<sub>6</sub>{μ-(Ph<sub>2</sub>P)<sub>2</sub>NH}<sub>4</sub>(μ<sub>3</sub>-SePh)<sub>4</sub>](BF<sub>4</sub>)<sub>2</sub>
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A series of trinuclear copper(I) thiolate complexes, [Cu3(μ-dppm)3(μ3-SR)2]BF4 (R = C6H4Cl-4, C6H4CH3-4, C6H4OCH3-4, C6H4(OCH3)2-3,4, C6H4-benzo-15-crown-5, or tBu), [Cu3(μ-dppm)3(μ3-StBu)](BF4)2, and [Cu3(μ-dppm)3(μ3-SR)(μ3-Cl)]BF4 (R = C6H4CH3-4, C6H4tBu-4, or C6H4(CH3)3-2,4,6) and two hexanuclear copper(I) selenolate complexes, [Cu6(μ-P∧P)4(μ3-SePh)4](BF4)2 (P∧P = dppm, (Ph2P)2NH), have been synthesized, and their photophysical properties have been studied. The X-ray crystal structures of both copper(I) selenolate complexes have been determined. These complexes have been shown to exhibit long-lived low-energy emission in solution, attributed to an excited state of predominantly ligand-to-metal charge-transfer [chalcogenolate to copper(I)] origin.
