Synthesis, photophysics, and electrochemistry of hexanuclear silver(I) chalcogenolate complexes. X-ray crystal structures of [Ag6(μ-dppm)4-(μ3-SC6H 4Me-p)4](PF6)2 and [Ag6(μ-dppm)4(μ3-SeC6H 4Cl-p)4](PF6)2

Abstract

A series of unprecedented hexanuclear silver(I) chalcogenolate complexes with bridging dppm ligands, [Ag6(μ-dppm)4(μ3-EAr)4](PF 6)2 (EAr = SPh 1, SC6H4Me-p 2, SePh 3, SeC6H4Cl-p 4), have been synthesized and characterized. The X-ray crystal structures of 2 and 4 have been determined. The complexes were found to exhibit luminescence at 77 K and the orange-red emission was tentatively attributed to originate from excited states of an admixture of metal-centred (MC) and metal···metal-bond-to-ligand charge-transfer (MMLCT) character. The complexes were also found to exhibit interesting fluxional behaviour in solution and the weak Ag···Ag interaction is believed to play an important role in governing their fluxional properties.