Syntheses, Photophysics, and Photochemistry of Trinuclear Copper(I) Thiolate and hexanuclear Copper(I) selenolate Complexes: X-ray Crystal Structures of [Cu_6(#mu#-dppm)_4(#mu#_3-SePh)_4](BF_4)_2 and [Cu_6{#mu#-(Ph_2P)_2NH}_4(#mu#_3-SePh)_4](BF_4)_2

摘要

A series of trinuclear copper(I) thiolate complexes, [Cu_3(#mu#-dppm)_3(#mu#_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 ~tBu), [Cu_3(#mu#-dppm)_3(#mu#_3-s~tBu)](BF_4)_2, and [Cu_3(#mu#-dppm)_3(#mu#_3-SR)(#mu#_3-Cl)]BF_4 (R = C_6H_4CH_3-4, C_6H_4~tBu-4, or C_6H_4(CH_3)_3-2,4,6) and two hexanuclear copper(I) selenolate coplexes, [Cu_6(#mu#-P~^P)_4(#mu#_3-SePh)_4(BF_4)_2 (P~^P = 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-enery emission in solution, attributed to an excited state of predominantly ligand-to-metal charge-transfer [chalocgenolate to copper(I)] origin.