Isolation, structure and spectroscopic characterization of silver complexes of the zwitterionic thiolate Tab: [Ag(Tab)2](PF6), {[Ag3(Tab)4](PF6)3 · 2DMF}n, and [Ag14(μ6-S)(Tab)12(PPh3)8](PF6)12(Tab=4-(trimethylammonio)benzenethiolate)

Reactions of Ag(PPh3)2Cl with equimolar TabHPF6 (TabH=4-(trimethylammonio)benzenethiol) under the presence of Et3N in CH3OH/CH2Cl2 afforded a mononuclear complex [Ag(tab)2](PF6) (1). Treatment of 1 with excess Na2S in CH3CN/DMF gave rise to a unusual one-dimensional polymer {[Ag3(tab)4](PF6)3 · 2DMF}n (2) as a major product and a netradecanuclear cage-like cluster [Ag14(μ6-S)(Tab)12(PPh3)8](PF6)12 (3) as a minor product. Compounds 1 and 2 were characterized by elemental analysis, IR, UV–Vis, and X-ray analysis. The Ag atom of the [Ag(Tab)2]+ cation of 1 adopts a linear AgS2 coordination geometry. Compound 2 has an one-dimensional chain structure in which the repeating [Ag6(Tab)8]6+ units are interconnected by four Ag–S bonds with [PF6]− anions and DMF solvated molecules located between the polymeric chains. The structure of the [Ag14(μ6-S)(tab)12(PPh3)8]12+ dodecation of 3 consists of a μ6-sulfur atom encapsulated by an Ag14S12 cage. The luminescence properties of 1 and 2 in solution and in the solid state at room temperature are also reported.