A DFT investigation of the structure/electron count relationship in an electron-rich copper nanocluster with unprecedented Cu39superatomic core

Abstract

This paper reports a DFT computational analysis of the richest in electron ever known thiolate-protected copper nanocluster that was recently reported by Liu, Huang and coworkers as being [Cu75(S-Adm)32]2+. Our calculations suggest that this compound is most likely the closed-shell trication [Cu75(S-Adm)32]3+ and that it is a 40-electron superatom with the 1S2 1P6 1D10 2S2 1F14 2P6 configuration. This electron count is associated with an unprecedented multishell [Cu39]- = Cu@Cu14(tetrakis hexahedron)@Cu24(truncated octahedron) superatomic core. This core is protected by 32 thiolate ligands and 36 Cu(I) metal centers which are coordinated to two or three sulfur lone pairs.