Isolation, structure and spectroscopic characterization of silver complexes of the zwitterionic thiolate Tab:: [Ag3(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)(2)Cl with equimolar TabHPF(6) (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 {[Ag-3(tab)(4)](PF6)(3) (.) 2DMF}(n) (2) as a major product and a netradecanuclear cage-like cluster [Ag-14(mu(6)-S)(Tab)(12)(PPh3)(8)](PF6)(12) (3) as a minor product. Compounds I and 2 were characterized by elemental analysis, IR, UV-Vis, and X-ray analysis. The Ag atom of the [Ag(Tab)(2)](+) cation of I adopts a linear AgS2 coordination geometry. Compound 2 has an one-dimensional chain structure in which the repeating [Ag-6(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 [Ag-14(mu(6)-S)(tab)(12)(PPh3)(8)](12+) dodecation of 3 consists of a mu(6)-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. (C) 2004 Elsevier B.V. All rights reserved.