Department of Chemistry, National Dong Hwa University, No. 1, Sec. 2, Da Hsueh Rd. Shoufeng, Hualien, 97401, Taiwan R.O.C.
UMR-CNRS, 6226 ", Institut des Sciences Chimiques de Rennes", University de Rennes 1, 35042, Rennes Cedex, France.
Angew Chem Int Ed Engl. 2017 Aug 14;56(34):10178-10182. doi: 10.1002/anie.201704800. Epub 2017 Jun 12.
The first atomically and structurally precise silver-nanoclusters stabilized by Se-donor ligands, [Ag {Se P(O Pr) } ] (3) and [Ag {Se P(OEt) } ] (4), were isolated by ligand replacement reaction of [Ag {S P(O Pr) } ] (1) and [Ag {S P(O Pr) } ] (2), respectively. Furthermore, doping reactions of 4 with Au(PPh )Cl resulted in the formation of [AuAg {Se P(OEt) } ] (5). Structures of 3, 4, and 5 were determined by single-crystal X-ray diffraction. The anatomy of cluster 3 with an Ag core having C symmetry is very similar to that of its dithiophosphate analogue 1. Clusters 4 and 5 exhibit an Ag and Au@Ag core of O symmetry composed of eight silver capping atoms in a cubic arrangement and encapsulating an Ag and Au@Ag centered icosahedron, respectively. Both ligand exchange and heteroatom doping result in significant changes in optical and emissive properties for chalcogen-passivated silver nanoparticles, which have been theoretically confirmed as 8-electron superatoms.
通过配体取代反应分别分离得到了由 Se 供体配体稳定的具有原子和结构精确的银纳米簇 [Ag{SeP(O Pr )} ]（3）和[Ag{SeP(OEt )} ]（4）。此外，掺杂反应使 4 与 Au(PPh )Cl 反应，生成 [AuAg{SeP(OEt )} ]（5）。通过单晶 X 射线衍射确定了 3、4 和 5 的结构。具有 C 对称性的 Ag 核的 3 簇的结构与相应的二硫代磷酸酯类似物 1 非常相似。簇 4 和 5 分别具有 Ag 和 Au@Ag 核的 O 对称性，由八个立方排列的银帽原子组成，并分别封装一个 Ag 和 Au@Ag 中心的二十面体。配体交换和杂原子掺杂导致硫属元素封端的银纳米粒子的光学和发光性质发生显著变化，这些变化已在理论上被确认为 8 电子超原子。
