Does the “Superatom” Exist in Halogenated Aluminum Clusters?

We have shown that Aln clusters do not show any characteristics of a superatom in halogenated aluminum clusters. The enhanced stability of halogenated Al clusters can be explained by the magic nature of the clusters, not by superatom chemistry. The presence of even a few electronegative elements provides significant perturbation to the molecular orbitals of Al clusters and stabilizes the electropositive Al cluster cores, closely correlating with metal cluster−ligand chemistry. Our work provides significant chemical insights into the understanding of the structure and stability of halogenated aluminum clusters, and these new insights are applicable to other metal cluster−ligand systems.