[Au16Ag43H12(SPhCl2)34]5-: An Au-Ag Alloy Nanocluster with 12 Hydrides and Its Enlightenment on Nanocluster Structural Evolution

Xiao Wei; Xi Kang; Tengfei Duan; Hao Li; Shuxin Wang; Yong Pei; Manzhou Zhu

doi:10.1021/acs.inorgchem.1c01624

[Au₁₆Ag₄₃H₁₂(SPhCl₂)₃₄]^5-: An Au-Ag Alloy Nanocluster with 12 Hydrides and Its Enlightenment on Nanocluster Structural Evolution

Inorg Chem. 2021 Aug 2;60(15):11640-11647. doi: 10.1021/acs.inorgchem.1c01624. Epub 2021 Jul 21.

Authors

Xiao Wei¹, Xi Kang¹, Tengfei Duan², Hao Li¹, Shuxin Wang¹, Yong Pei², Manzhou Zhu¹

Affiliations

¹ 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.
² Department of Chemistry, Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, Xiangtan University, Xiangtan 411105, P. R. China.

PMID: 34286977
DOI: 10.1021/acs.inorgchem.1c01624

Abstract

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-[Au₁₆Ag₄₃H₁₂(SPhCl₂)₃₄]^5-. The structure of [Au₁₆Ag₄₃H₁₂(SPhCl₂)₃₄]^5- comprises an Au₁₆Ag₃ kernel that is stabilized by 12 hydride ligands, 8 thiol bridges, and 6 Ag_m(SR)_n motif units. The 12 hydride ligands in Au₁₆Ag₄₃ have been confirmed by both ²H NMR and ESI-MS measurements, and their positions have been theoretically evaluated, located at the interlayer between the Au₁₆Ag₃ kernel and the Ag-SR shell. The metastable [Au₁₆Ag₄₃H₁₂(SPhCl₂)₃₄]^5- can convert to [Au₁₂Ag₃₂(SPhCl₂)₃₀]^4- spontaneously. Structurally, the Au₁₆Ag₃ kernel of [Au₁₆Ag₄₃H₁₂(SPhCl₂)₃₄]^5- could be regarded as the overlapping of two hollow Au₈Ag₃ cages via sharing an Ag₃ line, which is in contrast to the solely icosahedral Au₁₂ kernel of [Au₁₂Ag₃₂(SPhCl₂)₃₀]^4-. Besides, the overall construction of Au₁₆Ag₄₃ or Au₁₂Ag₃₂ follows a complementing or overlapping assembly mode, respectively. Overall, the structural anatomy of Au₁₆Ag₄₃H₁₂(SPhCl₂)₃₄ sheds some new insight into the structural evolution of metal nanoclusters.