A DFT investigation of the structure/electron count relationship in an electron-rich copper nanocluster with unprecedented Cu$_39$ superatomic core
Résumé
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.
Origine | Fichiers produits par l'(les) auteur(s) |
---|