Wei Xiao, Kang Xi, Duan Tengfei, Li Hao, Wang Shuxin, Pei Yong, Zhu Manzhou
Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Anhui University, Hefei 230601, P. R. China.
Department of Chemistry, Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, Xiangtan University, Xiangtan 411105, P. R. China.
Inorg Chem. 2021 Aug 2;60(15):11640-11647. doi: 10.1021/acs.inorgchem.1c01624. Epub 2021 Jul 21.
The structural determination of alloy hydride nanoclusters with high nuclearity remains challenging. We herein report the synthetic procedure and the structural elucidation of an Au-Ag alloy nanocluster with 12 hydride ligands-[AuAgH(SPhCl)]. The structure of [AuAgH(SPhCl)] comprises an AuAg kernel that is stabilized by 12 hydride ligands, 8 thiol bridges, and 6 Ag(SR) motif units. The 12 hydride ligands in AuAg have been confirmed by both H NMR and ESI-MS measurements, and their positions have been theoretically evaluated, located at the interlayer between the AuAg kernel and the Ag-SR shell. The metastable [AuAgH(SPhCl)] can convert to [AuAg(SPhCl)] spontaneously. Structurally, the AuAg kernel of [AuAgH(SPhCl)] could be regarded as the overlapping of two hollow AuAg cages via sharing an Ag line, which is in contrast to the solely icosahedral Au kernel of [AuAg(SPhCl)]. Besides, the overall construction of AuAg or AuAg follows a complementing or overlapping assembly mode, respectively. Overall, the structural anatomy of AuAgH(SPhCl) sheds some new insight into the structural evolution of metal nanoclusters.
具有高核数的合金氢化物纳米团簇的结构测定仍然具有挑战性。我们在此报告了一种具有12个氢化物配体的Au-Ag合金纳米团簇[AuAgH(SPhCl)]的合成过程和结构解析。[AuAgH(SPhCl)]的结构包括一个由12个氢化物配体、8个硫醇桥和6个Ag(SR)基序单元稳定的AuAg核。AuAg中的12个氢化物配体已通过1H NMR和ESI-MS测量得到证实，其位置已通过理论评估，位于AuAg核与Ag-SR壳之间的层间。亚稳态的[AuAgH(SPhCl)]可以自发地转化为[AuAg(SPhCl)]。在结构上，[AuAgH(SPhCl)]的AuAg核可被视为两个空心AuAg笼通过共享一条Ag线的重叠，这与[AuAg(SPhCl)]仅有的二十面体Au核形成对比。此外，AuAg或AuAg的整体构建分别遵循互补或重叠的组装模式。总体而言，AuAgH(SPhCl)的结构剖析为金属纳米团簇的结构演化提供了一些新的见解。
