A DFT investigation of the structure/electron count relationship in an electron-rich copper nanocluster with unprecedented Cu39 superatomic core

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 [Cu 75 (S-Adm) 32 ] 2 + . Our calculations suggest that this compound is most likely the closed -shell trication [Cu 75 (S-Adm) 32 ] 3 + and that it is a 40 -electron superatom with the 1S 2 1P 6 1D 10 2S 2 1F 14 2P 6 configuration. This electron count is associated with an unprecedented multishell [Cu 39 ] - = Cu@Cu 14 (- tetrakis hexahedron)@Cu 24 (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.