Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (7): 703-708.DOI: 10.6023/A23030078 Previous Articles     Next Articles

Article

Pd和Hg共掺杂的金属纳米团簇HgPdAu23(PET)18

张玉莹a, 蔡潇b, 胡维刚b, 李光俊b, 祝艳b,*()   

  1. a 运城学院应用化学系 运城 044000
    b 南京大学化学化工学院 南京 210023
  • 投稿日期:2023-03-13 发布日期:2023-06-05
  • 作者简介:
    庆祝《化学学报》创刊90周年.
  • 基金资助:
    运城学院优秀博士来晋科研项目(QZX-2023008); 中国博士后基金(2022M721551)

Pd and Hg Atoms Co-doped HgPdAu23(PET)18 Nanocluster

Yuying Zhanga, Xiao Caib, Weigang Hub, Guangjun Lib, Yan Zhub()   

  1. a Department of Applied Chemistry, Yuncheng University, Yuncheng 044000
    b School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023
  • Received:2023-03-13 Published:2023-06-05
  • Contact: *E-mail: zhuyan@nju.edu.cn
  • About author:
    Dedicated to the 90th anniversary of Acta Chimica Sinica.
  • Supported by:
    Outstanding Doctoral Research Project of Yuncheng University(QZX-2023008); China Postdoctoral Foundation(2022M721551)

The introduction of heteroatoms into metal nanoclusters is an effective strategy to regulate the physical and chemical properties of clusters. Most of the doped clusters reported are binary metal nanoclusters via one metal heteroatom doping into a metal nanocluster, while the preparation and properties of ternary metal nanoclusters via two heteroatoms doping into a metal nanocluster are rarely studied. In this work, we report the Pd and Hg co-doped ternary metal nanocluster HgPdAu23(PET)18 (PET=2-phenylethanethiol) using the Au25(PET)18 nanocluster as an ideal template that can be viewed as a Au13 icosahedral core protected by the exterior 12 Au atoms as a shell. The structural framework of the HgPdAu23(PET)18 nanocluster is similar to that of its parent Au25(PET)18 nanocluster, determined by single-crystal X-ray crystallography and electrospray ionization mass spectroscopy (ESI-MS), which shows a 13-atom icosahedral core and a 12-atom shell capped by 18 thiolate ligands. It indicated that the doping strategy might destroy the total structure (core plus surface) of the parent nanocluster, which will offer an excited opportunity for the correlation of the structure with properties of the doped nanoclusters. More notably, the possible doping location of the Pd and Hg atoms in the HgPdAu23(PET)18 nanocluster can be determined by the combination of single-crystal X-ray crystallography and nuclear magnetic resonance (NMR) spectroscopy (i.e., 1H NMR and two-dimentional NMR). It is suggested that the Pd atom is possibly located on the center of the icosahedron of the HgPdAu23(PET)18 nanocluster, while the Hg atom is possibly located on the surface of the icosahedron of the HgPdAu23(PET)18 nanocluster. The electronic configuration of HgPdAu23(PET)18 nanocluster is distinct from those of the parent Au25(PET)18 and one-metal doped PdAu24(PET)18 and HgAu24(PET)18 nanoclusters, which can be implied by the X-ray photoelectron spectroscopy (XPS) and UV-Vis absorption spectroscopy. This study provides a new design rule for the two-metal-heteroatom doped nanoclusters.

Key words: nanocluster, heteroatoms, doping, structure