Abstract
By the reaction of AgNO(3), 2-methyl-2-propanethiol (HStBu), with various-sized halogen ions as templates, three multi-nuclear silver-thiolate cluster-based chain-like coordination polymers, [Ag(6)(μ-SBu)(6)](n) (USC-CP-2), [Ag(6)(μ-StBu)(5)Br](n) (USC-CP-4) and [Ag(14)(μ-StBu)(12)I(2)](n) (USC-CP-3) constructed by different Ag(I)-nanocages, have been synthesized and characterized by X-ray diffraction analyses. With F(-), Cl(-) or without template, USC-CP-2 exhibits a one-dimensional structure composed of detached Ag(6)-cages, absent of fluoride or chloridion. While with Br(-) and I(-), USC-CP-4 and USC-CP-3, two distinct halogen-templating multi-sliver cages-based chain-like polymeric structures have been observed, which are a mono-Br(-) encapsulated Ag(8)-cage, or a dual-I(-) embedded Ag(16)-cage, respectively. In these three compounds, the multi-Ag(I) cages were self-assembled by Ag-S bonds through bridged μ(2)-StBu ligands, and stabilized argentophilic interactions between neighboring silver atoms. This study demonstrates that the halide anions of varying sizes play a critical role in inducing the nucleation and structural evolution of the silver-thiolate clusters.