New structural insights into the stability of Au22(SR)16 nanocluster under ring model guidance

Wenhua Han; Endong Wang; Wen Wu Xu

doi:10.1039/d2cp00421f

New structural insights into the stability of Au₂₂(SR)₁₆ nanocluster under ring model guidance

Phys Chem Chem Phys. 2022 Jul 6;24(26):15920-15924. doi: 10.1039/d2cp00421f.

Authors

Wenhua Han¹, Endong Wang^{2

3}, Wen Wu Xu¹

Affiliations

¹ Department of Physics, School of Physical Science and Technology, Ningbo University, Ningbo, 315211, China. xuwenwu@nbu.edu.cn.
² School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian, 116029, China. edwang@lnnu.edu.cn.
³ State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.

PMID: 35758327
DOI: 10.1039/d2cp00421f

Abstract

This study presents thorough structural insights into the stability of crystallized Au₂₂(SAdm)₁₆ (HSAdm = 1-adamantanethiol) nanocluster. With the recently developed Ring Model for describing the interaction between inner gold cores and outer protecting ligands in thiolate-protected gold nanoclusters, the experimental spontaneous transformation from the crystallized Au₂₂(SAdm)₁₆ to Au₂₁(SAdm)₁₅ could be well understood as structurally unfavorable for the current Au₂₂(SAdm)₁₆ and could also be attributed to the weaker aurophilic interaction between the inner Au₄ core and the surrounding rings in Au₂₂(SAdm)₁₆ over that in Au₂₁(SAdm)₁₅. Furthermore, with the Ring Model and the grand unified model, two new Au₂₂(SCH₃)₁₆ isomers with evident lower energies, higher HOMO-LUMO gaps as well as distinct optical properties over the available crystallized isomer were obtained. This study deepens the current knowledge on the structure of the Au₂₂(SR)₁₆ cluster from a new structural point of view and also confirms the validity as well as practicability of the Ring Model in understanding and predicting the stable structures of thiolate-protected gold nanoclusters.