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

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.