School of Chemistry and Pharmaceutical Sciences, Guangxi Key Laboratory of Low Carbon Energy Materials, Guangxi Normal University, Yu Cai Road 15, Qi Xin District, Guilin 541004, Guangxi, China.
Nanoscale. 2018 Jan 3;10(2):515-519. doi: 10.1039/c7nr07308a.
A first and stable Ag-P superatom nanocluster Ag(N-triphos)(Cl) (1) has been successfully synthesized and characterized. X-ray analysis shows that this Ag cluster has a hexacapped body-centered cubic (bcc) framework which is consolidated by four tripodal N-triphos ligands. The identity of 1 is confirmed by high resolution ESI-MS. Cluster 1 has an electronic and geometric shell closure structure with 8 free electrons, matching the stability idea of superatom theory for a nanocluster. DFT calculation of this Ag cluster reveals the superatom feature with a 1S1P configuration. The chelation of multidentate phosphines enhances the stability of this Ag cluster. The AgAg distances between the centered and the vertical Ag atoms of this bcc (Ag@Ag) are in the range of 2.57-2.71 Å, and the distances between the face-capped and the vertical silver atoms are in the range of 2.84-2.92 Å, showing strong AgAg interactions within this cluster core. This superatom complex exhibits a relatively high thermal and photolytic stability.
已成功合成并表征了首个稳定的 Ag-P 超原子纳米团簇 Ag(N-triphos)(Cl)（1）。X 射线分析表明，该 Ag 团簇具有由四个三脚型 N-triphos 配体稳定的六面心立方（bcc）骨架。高分辨率 ESI-MS 证实了 1 的身份。该簇具有 8 个自由电子的电子和几何壳层封闭结构，符合纳米团簇超原子理论的稳定性思想。该 Ag 团簇的 DFT 计算揭示了具有 1S1P 构型的超原子特征。多齿膦的螯合增强了该 Ag 团簇的稳定性。该 bcc（Ag@Ag）中中心和垂直 Ag 原子之间的 AgAg 距离在 2.57-2.71 Å 范围内，而面封端和垂直银原子之间的距离在 2.84-2.92 Å 范围内，表明该团簇核内存在强烈的 AgAg 相互作用。该超原子配合物表现出较高的热稳定性和光解稳定性。
