Ab initio study of luminescent chalcogenido silver(I) clusters [Ag4(μ-H2PCH2PH2) 4(μ4-E)]2+

Ab initio calculations have been performed on the chalcogenido silver(I) model complexes [Ag4(μ-H2PCH2PH2)4(μ4-E)]2+ and their cores [Ag4(μ4-E)]2+ (E = S, Se and Te) at the RHF/3-21G level. The results reveal a chalcogenido-based HOMO and metal-based LUMO. It is envisaged that the excited states of luminescent silver(I) clusters [Ag4-(μ-dppm)4-(μ4-E)]2+ bear a high parentage of ligand-to-metal charge-transfer LMCT (E2− → Ag4) character, mixed with a metal-centred MC (ds/dp) state.