D6h‐Au42 Isomer: A Golden Aromatic Toroid Involving Superatomic π‐Orbitals that Follow the Hückel (4n+2)π rule

Recently, it has been shown that the superatom concept is intimately connected to relevant tools of great chemical significance, such as the Lewis structure model and the VSEPR theory, which has been employed to understand hybridized and dimeric‐like molecules. This suggests a potential rational construction of superatomic clusters mimicking more complex structures. Here, we extend another well‐employed concept to the superatomic clusters, to construct a novel Au₄₂ isomer with resemblance to cyclic aromatic molecules. It is shown that the Hückel (4n+2)π rule is ready to be applied, predicting aromatic behavior latterly supported by the favorable evaluation of the induced shielding cone formation. The D₆h isomer of Au₄₂ described here exhibits inherent characteristics mimicking aromatic hydrocarbon rings, displaying π‐superatomic orbitals and related properties. This new cluster is the first member of the superatomic clusters family to exhibit an aromatic π‐electron system.