Superatomic molecules: natural and non-natural atom-like bonding between superatoms

Abstract Superatomic molecules, formed by the fusion or combination of spherical metal nanoclusters (superatoms), have emerged as a novel framework for understanding the stability of anisotropic metal nanoclusters. Advances in the synthesis and structural characterization of these anisotropic clusters have provided valuable insights into the classification of superatomic molecules and the development of a corresponding bonding theory. This review offers a qualitative perspective on the relationship between molecular geometry and electronic structure in superatomic molecules, focusing on superatomic molecular orbitals formed through the linear combination of individual superatomic orbitals—analogous to atomic orbitals in natural molecules. Unique stabilization features, not observed in conventional molecular systems, are also highlighted. Furthermore, the review discusses potential functional properties of superatomic molecules in the context of future applications.