Yuan Shang-Fu, Guan Zong-Jie, Liu Wen-Di, Wang Quan-Ming
Department of Chemistry, Tsinghua University, 100084, Beijing, China.
Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, 361005, Xiamen, China.
Nat Commun. 2019 Sep 6;10(1):4032. doi: 10.1038/s41467-019-11988-y.
Surface organic ligands are critical in determining the formation and properties of atomically precise metal nanoclusters. In contrast to the conventionally used thiolate, phosphine and alkynyl ligands, the amine ligand dipyridylamine is applied here as a protecting agent in the synthesis of atomically precise metal nanoclusters. We report two homoleptic amido-protected Ag nanoclusters as examples of all-nitrogen-donor-protected metal nanoclusters: [Ag(dpa)]SbF (Ag) and Ag(dpa) (Ag) (dpa = dipyridylamido). Single crystal X-ray structural analysis reveals that both clusters consist of a centered-icosahedron Ag core wrapped by 12 dpa ligands. The flexible arrangement of the N donors in dpa facilitates the solvent-triggered reversible interconversion between Ag and Ag due to their very different solubility. The successful use of dpa in the synthesis of well-defined silver nanoclusters may motivate more studies on metal nanoclusters protected by amido type ligands.
表面有机配体对于确定原子精确的金属纳米团簇的形成和性质至关重要。与传统使用的硫醇盐、膦和炔基配体不同，胺配体二吡啶胺在此被用作原子精确的金属纳米团簇合成中的保护剂。我们报道了两个同配体酰胺保护的银纳米团簇，作为全氮供体保护的金属纳米团簇的例子：[Ag(dpa)]SbF (Ag₁₂) 和 [Ag(dpa)]₁₂(SbF₆)₄ (Ag₂₄)（dpa = 二吡啶酰胺）。单晶X射线结构分析表明，两个团簇均由一个被12个dpa配体包裹的中心二十面体银核组成。由于其溶解性差异很大，dpa中氮供体的灵活排列促进了Ag₁₂和Ag₂₄之间由溶剂触发的可逆相互转化。dpa在合成明确的银纳米团簇中的成功应用可能会激发更多关于酰胺型配体保护的金属纳米团簇的研究。
