Synthesis, structures, and photophysics of polynuclear silver(I) thiolate and silver(I) thiocarboxylate complexes with dppm ligands

Abstract

Trinuclear silver(I) thiolate and silver(I) thiocarboxylate complexes [Ag 3(μ-dppm) 3(μ n-SR) 2] (ClO 4) [n = 2, R = C 6H 4Cl-4 (1) and C{O}Ph (2); n = 3, R = tBu (3)], pentanuclear silver(I) thiolate complex [Ag 5(μ-dppm) 4(μ 3-SC 6H 4NO 2-4) 4](PF 6) (4), and hexanuclear silver(I) thiolate complexes [Ag 6(μ-dppm) 4(μ 3-SR) 4]Y 2 [Y = ClO 4, R =C 6H 4CH 3-4 (5) and C 10H 7 (2-naphthyl) (7); Y = PF 6, R = C 6H 4OCH 3-4(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. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.