Toward Understanding the Correlation between the Charge States and the Core Structures in Thiolate-Protected Gold Nanoclusters

Yuxin Liu; Wenhua Han; Zeen Hong; Wen Wu Xu; Endong Wang

doi:10.1021/acs.jpclett.2c01306

Toward Understanding the Correlation between the Charge States and the Core Structures in Thiolate-Protected Gold Nanoclusters

J Phys Chem Lett. 2022 Jun 23;13(24):5387-5393. doi: 10.1021/acs.jpclett.2c01306. Epub 2022 Jun 9.

Authors

Yuxin Liu¹, Wenhua Han¹, Zeen Hong¹, Wen Wu Xu¹, Endong Wang²

Affiliations

¹ Department of Physics, School of Physical Science and Technology, Ningbo University, Ningbo 315211, China.
² School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, China.

PMID: 35678557
DOI: 10.1021/acs.jpclett.2c01306

Abstract

The charge states of thiolate-protected gold nanoclusters (AuNCs) are vital to their stabilities through affecting the number of the valence electrons. However, the origin of the charge states of AuNCs has not been fully understood yet. Herein, through fulfilling the duet-rule derived Au₃(2e) and Au₄(2e) elementary blocks in the grand unified model (GUM), analysis on the substantial crystal structures indicates the charge states of AuNCs can correlate with their core structural packing, especially the number of Au₃(2e) elementary blocks. In addition, aided by the Au₃(2e) block's role in tailoring the population of valence electron, three new AuNCs including Au₁₈(SCH₃)₁₄, Au₃₀(SCH₃)₂₀, and [Au₃₀(SCH₃)₂₁]^- are predicted through controllably specifying the exact number of Au₃(2e) in the core. This work shows that GUM can bridge the gap among the charge states of the cluster, the inner core structure of the cluster, and the detachment of outer ligands via the electron counting rule.