Peculiar All-Metal σ-Aromaticity of the [Au2Sb16]4- Anion in the Solid State

Gas-phase clusters are deemed to be sigma-aromatic when they satisfy the 4n+2 rule of aromaticity for delocalized sigma electrons and fulfill other requirements known for aromatic systems. While the range of nvalues was shown to be quite broad when applied to short-lived clusters found in molecular-beam experiments, stability of all-metal cluster-like fragments isolated in condensed phase was previously shown to be mainly ascribed to two electrons (n=0). In this work, the applicability of this concept is extended towards solid-state compounds by demonstrating a unique example of a storable compound, which was isolated as a stable [K([2.2.2]crypt)](+) salt, featuring a [Au2Sb16](4-) cluster core possessing two all-metal aromatic AuSb4 fragments with six delocalized sigma electrons each (n=1). This discovery pushes the boundaries of the original idea of Kekule and firmly establishes the usefulness of the sigma-aromaticity concept as a general idea for both small clusters and solid-state compounds.