On the variation of cluster core characteristics by an endohedral atom. Shape variation in 8-ce [EAu 4 (PPh 3 ) 4 ] 2+ (E = N, P, As, Sb) clusters

• Published in: Physical chemistry chemical physics : PCCP Vol. 26; no. 30; pp. 20701 - 20708
• Main Authors: Guajardo-Maturana, Raul, MacLeod Carey, Desmond, Rodríguez-Kessler, Peter L, Muñoz-Castro, Alvaro
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 31.07.2024
• Subjects: Clusters
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d4cp01465k

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 [Au N(PPh ) ] and [Au Sb(PPh ) ] clusters denotes two contrasting shapes featuring a tetrahedral and square pyramidal structure, respectively. Herein, we further explore the [Au E(PPh ) ] (E = N, P, As, Sb) series in order to evaluate energetic and structural factors determining the overall shape. Our results show a favorable [Au (PPh ) ] /E 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.