All-Carboxylate-Protected Superatomic Silver Nanocluster with an Unprecedented Rhombohedral Ag8 Core

We report the synthesis and structure of the first all-carboxylate-protected superatomic silver nanocluster. It was prepared by heating a dimethylformamide solution of perfluoroglutaric acid and AgNO₃ under alkaline conditions, yielding a single crystal of [(CH₃)₂NH₂]₆[Ag₈(pfga)₆]. The [Ag₈(pfga)₆]^6- cluster has a rhombohedral Ag₈⁶⁺ core, with each of its faces protected by one dianionic perfluoroglutarate (pfga) ligand. Electronic-structure analysis from density functional theory confirms the stability of this two-electron cluster due to the shell closing of the superatomic orbital in the (1S)² configuration and explains the optical absorption of the cluster in the visible region as the transition from 1S to 1P orbital. The [Ag₈(pfga)₆]^6- cluster emits bright green-yellow light in THF solution and bright orange light in the solid state. This work opens the door to using the widely available carboxylic acids to synthesize atomically precise Ag clusters of attractive properties.