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

Ling Yang , Xin-Yao Wang , Xiao-Yan Tang , Meng-Yi Wang , Chun-Yan Ni , Hong Yu , Ying-Lin Song , Brendan F. Abrahams , 

Jian-Ping Lang

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.

温度依赖性氯化物介导的原子级硫醇银纳米团簇的获取

通过使用独特的温度依赖性、氯化物介导的方法，两个原子级的银纳米团簇[Cl@Ag14(Tab)12-(C5H4NCl)12](PF6)13(Cl@Ag14) 和[Cl3@Ag24(Tab)20(C5H4NCl)11]Cl(PF6)20(Cl3@Ag24)(Tab = 4-(tnmethylammomo)benzothiolate, C 5 H 4NCl = 3-氯吡啶）成功获得。值得注意的是，包裹在 Ag-S 壳内的氯离子的数量可以通过在不同温度下几乎不溶的 KCl 的缓慢溶解来调节。包含额外的核心氯离子导致周围 Ag-S 壳的膨胀。本文提供了一种有前景的合成方法，用于控制围绕阴离子核形成壳的 Ag 原子数量，此外还提供了将其他无机阴离子引入银簇的潜在途径。更广泛地说，通过使用相关配体，合成策略为生成不同大小和组成的硫醇银簇的新家族提供了空间。

DOI: 10.1007/s11426-022-1216-2