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Updated: Aug 13, 2025
Synthesis of Single-Crystalline Core-Shell Metal-Organic Frameworks
Published on: February 10, 2023
High-nuclearity and thiol protected core-shell [Cu75(S-Adm)32]2+: distorted octahedra fixed to Cu15 core via strong
Jie Tang1,2, Chong Liu3, Chenyu Zhu1
1Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China. chaoliu@dicp.ac.cn.
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.
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