Abstract

Atomically precise gold superatoms have attracted interest owing to their suitable use as building blocks for cluster-assembled materials, favoring ordered structures with advanced properties. In this sense, expanding their versatility is a relevant issue for controlling their properties and retaining a specific nuclearity. Interestingly, the reported structure for isoelectronic [Au4N(PPh3)(4)](+) and [Au4Sb(PPh3)(4)](+) clusters denotes two contrasting shapes featuring a tetrahedral and square pyramidal structure, respectively. Herein, we further explore the [Au4E(PPh3)(4)](+) (E = N, P, As, Sb) series in order to evaluate energetic and structural factors determining the overall shape. Our results show a favorable [Au-4(PPh3)(4)](4+)/E3- interaction energy, predicting particular patterns in their UV-vis spectrum. Thus, the use of dopant atoms is enabled to vary the core shape and, in turn, to modify the cluster properties, which serve as a structural control, in addition to ligand-based and size approaches.