High-nuclearity and thiol protected core–shell [Cu75(S-Adm)32]2+: distorted octahedra fixed to Cu15 core via strong cuprophilic interactions

Jie Tang; Chong Liu; Chenyu Zhu; Keju Sun; He Wang; Wen Yin; Chuting Xu; Yang Li; Weiguo Wang; Li Wang; Renan Wu; Chao Liu; Jiahui Huang

doi:10.1039/D2NR05921E

High-nuclearity and thiol protected core–shell [Cu₇₅(S-Adm)₃₂]²⁺: distorted octahedra fixed to Cu₁₅ core via strong cuprophilic interactions†

Jie Tang,^af Chong Liu,

^b Chenyu Zhu,^a Keju Sun,^c He Wang,^a Wen Yin,^a Chuting Xu,^d Yang Li,^d Weiguo Wang,^d Li Wang,^e Renan Wu,^e Chao Liu

*^a and Jiahui Huang

*^a

Author affiliations

* Corresponding authors

^a Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
E-mail: chaoliu@dicp.ac.cn

^b School of Chemical Engineering, Sichuan University, Chengdu 610065, China

^c College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004, China

^d Center for Advanced Mass Spectrometry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

^e Laboratory of High-Resolution Mass Spectrometry Technologies, CAS Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

^f University of Chinese Academy of Sciences, Beijing 100049, China

Abstract

Atomically precise nanoclusters have a critical role in understanding the structure–property relationships at the atomic level. Copper nanoclusters have attracted considerable attention, but the synthesis is limited because of susceptibility to oxidation. Herein, we developed a reduction speed controlling method to synthesize [Cu₇₅(S-Adm)₃₂]²⁺ (HS-Adm: 1-Adamantanethiol) nanocluster and reveal the key steps in the nucleation process. Cu₇₅ was first observed and characterized with the following features: (i) composed of a face-centered cubic Cu₁₅ kernel and a Cu₆₀ caged shell including 12 distorted octahedra. (ii) The observation of the shortest Cu–Cu bond (2.166(7) Å) in the Cu nanoclusters, which could result from the distortion of the octahedron. (iii) The sole μ³-S mode of S, which plays two roles as a vertex and bridge atom to connect Cu atoms. This work presents a unique nanoball Cu nanocluster with strong cuprophilic interaction and provides a novel method to expand the family of Cu nanoclusters as well.

Nanoscale

High-nuclearity and thiol protected core–shell [Cu₇₅(S-Adm)₃₂]²⁺: distorted octahedra fixed to Cu₁₅ core via strong cuprophilic interactions†

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High-nuclearity and thiol protected core–shell [Cu₇₅(S-Adm)₃₂]²⁺: distorted octahedra fixed to Cu₁₅ core via strong cuprophilic interactions

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