Density functional theory and thermodynamics analysis of MAl Keggin substitution reactions: Insights into ion incorporation and experimental confirmation.

Polyaluminum cations, such as the MAl Keggin, undergo atomic substitutions at the heteroatom site (M), where nanoclusters with M = Al, Ga, and Ge have been experimentally studied. The identity of the heteroatom M has been shown to influence the structural and electronic properties of the nanocluster and the kinetics of ligand exchange reactions. To date, only three ε-analogs have been identified, and there is a need for a predictive model to guide experiment to the discovery of new MAl species.