Synthesis, Structures, and Photophysics of Polynuclear Silver(I) Thiolate and Silver(I) Thiocarboxylate Complexes with Dppm Ligands

Abstract

AbstractTrinuclear silver(I) thiolate and silver(I) thiocarboxylate complexes [Ag3(μ‐dppm)3(μn‐SR)2](ClO4) [n = 2, R = C6H4Cl‐4 (1) and C{O}Ph (2); n = 3, R = tBu (3)], pentanuclear silver(I) thiolate complex [Ag5(μ‐dppm)4(μ3‐SC6H4NO2‐4)4](PF6) (4), and hexanuclear silver(I) thiolate complexes [Ag6(μ‐dppm)4(μ3‐SR)4]Y2 [Y = ClO4, R =C6H4CH3‐4 (5) and C10H7 (2‐naphthyl) (7); Y = PF6, R = C6H4OCH3‐4(6)], were synthesized [dppm = bis(diphenylphosphanyl)methane] and their crystal structures as well as photophysical properties were studied. In the solid state at 77 K, trinuclear silver(I) thiolate and silver(I) thiocarboxylate complexes 1 and 2 exhibit luminescence at 470–523 nm, tentatively attributed to originate from the 3IL (intraligand) of thiolate or thiocarboxylate ligands, whereas hexanuclaer silver(I) thiolate complexes 5 and 7 produce dual emission, in which high‐energy emission is tentatively attributed to come from the 3IL of thiolate ligands and low‐energy emission is tentatively assigned to come from the admixture of metal···metal bond‐to‐ligand charge‐transfer (MMLCT) and metal‐centered (MC) excited states.