Temperature-dependent chloride-mediated access to atom-precise silver thiolate nanoclusters

By using a unique temperature-dependent, chloride-mediated approach, two atom-precise silver nanoclusters [Cl@Ag14(Tab)12-(C5H4NCl)12](PF6)13(Cl@Ag14) and [Cl3@Ag24(Tab)20(C5H4NCl)11]Cl(PF6)20(Cl3@Ag24) (Tab = 4-(tnmethylammomo)benzenethiolate, C5H4NCl = 3-chloropyridine) were obtained successfully. Notably, the number of chloride ions encapsulated inside the Ag-S shell could be regulated by the slow dissolution of almost insoluble KCl at various temperatures. The inclusion of additional core chloride ions results in the expansion of the surrounding Ag-S shell. This article provides a promising synthetic approach for controlling the number of Ag atoms that form a shell around the anionic core, in addition to offering a potential pathway for the introduction of other inorganic anions into silver clusters. More broadly, through the use of related ligands, the synthetic strategy offers scope for generating new families of silver thiolate clusters of varying size and composition.