Syntheses, photophysics, and photochemistry of trinuclear copper(I) thiolate and hexanuclear copper(I) selenolate complexes: X-ray crystal structures of [Cu6(μ3-dppm) 4(μ3-SePh)4](BF4)2 and [Cu6{μ-(Ph2P)2NH}4(μ3-SePh)4](BF4)2

Abstract

A series of trinuclear copper(I) thiolate complexes, [Cu 3(μ-dppm) 3(μ 3-SR) 2] BF 4 (R = C 6H 4Cl-4, C 6H 4CH 3-4, C 6H 4OCH 3-4, C 6H 4(OCH 3) 2-3,4, C 6H 4-benzo-15-crown-5, or ′Bu), [Cu 3(μ-dppm) 3(μ 3-S′Bu)] (BF 4) 2, and [Cu 3(μ-dppm) 3(μ 3-SR) (μ 3-Cl)]BF 4 (R = C 6H 4CH 3-4, C 6H 4′Bu-4, or C 6H 4(CH 3) 3-2,4,6) and two hexanuclear copper(I) selenolate complexes, [Cu 6(μ-PP) 4(μ 3-SePh) 4](BF 4) 2 (PP = dppm, (Ph 2P) 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.