[Au₇]³⁺: A Missing Link in the Four-Electron Gold Cluster Family

Abstract

Ligand-stabilized ultrasmall gold clusters offer a library of diverse geometrical and electronic structures. Among them, clusters with four valence electrons form an exceptional but interesting family because of their unique geometrical structures and optical properties. Here, we report a novel diphosphine-ligated four-electron Au₇ cluster (<b>2</b>). In good agreement with previous theoretical predictions, <b>2</b> has a “core+<i>one</i>” structure to exhibit a prolate shape. The absorption spectrum showed an isolated band, similar to the spectra of Au₆ and Au₈ clusters with “core+<i>two</i>” structures. TD-DFT studies demonstrated that the attachment of only one gold atom to a polyhedral core is sufficient to generate unique electronic structures and characteristic absorptions. The present result fills the missing link between Au₆ and Au₈ in the four-electron cluster family, showing that the HOMO–LUMO gap increases with increasing nuclearity in the case of the tetrahedron-based “core+<i>exo</i>” clusters