Unraveling the Nucleation Process from a Au(I)-SR Complex to Transition-Size Nanoclusters

Qinzhen Li; Baoyu Huang; Sha Yang; Hui Zhang; Jinsong Chai; Yong Pei; Manzhou Zhu

doi:10.1021/jacs.1c06354

Unraveling the Nucleation Process from a Au(I)-SR Complex to Transition-Size Nanoclusters

J Am Chem Soc. 2021 Sep 22;143(37):15224-15232. doi: 10.1021/jacs.1c06354. Epub 2021 Sep 9.

Authors

Qinzhen Li^{1

2}, Baoyu Huang³, Sha Yang¹, Hui Zhang², Jinsong Chai¹, Yong Pei³, 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 and Institutes of Physical Science and Information Technology, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Anhui University, Hefei, Anhui 230601, China.
² School of Physics and Materials Science, Anhui University, Hefei, Anhui 230601, China.
³ Department of Chemistry, Key Laboratory of Environmentally Friendly Chemistry and Applications of MOE, Xiangtan University, Xiangtan, Hunan 411105, China.

PMID: 34498861
DOI: 10.1021/jacs.1c06354

Abstract

Atomically precise noble metal nanoclusters provide a critical benchmark for the fundamental research of the origin of condensed matter because they retain the original state of the metal bonds. Also, knowledge about the transition from organometallic complexes to a nanoclusters is important for understanding the structural evolution of the nanoclusters, particularly their nucleation mechanism. Herein, three transition-size gold nanoclusters are prepared via a controlled diphosphine-mediated top-down routine. Starting from small-size nanoclusters, three new nanoclusters including Au₁₃(SAdm)₈(L⁴)₂(BPh₄) (Au₁₃), Au₁₄(S-c-C₆H₁₁)₁₀L⁴ (Au₁₄), and Au₁₆(S-c-C₆H₁₁)₁₁L^Ph* (Au₁₆) are obtained by controlled clipping on the surface and kernel of initial nanoclusters. Combining their atomically precise structures with DFT theoretical calculations, the overall atom-by-atom structural evolution process from Au₁₂(SR)₁₂ (0 e^-) to Au₁₈(SR)₁₄ (4 e^-) is mapped out. In addition, studies on their electronic structures show that the evolution from an organometallic complex to nanoclusters is accompanied by a dramatic decrease in the HOMO-LUMO gaps. Most importantly, the formation of the first Au-Au bond is captured in the "Au₄S₄ to Au₅" nucleation process from Au₁₂(SR)₁₂ complex to the Au₁₃ nanocluster. This work provides a deep insight into the origin of inner core in Au NCs and their structural transition relationship with metal complexes.