Abstract
Doping alkali metals into boron clusters can effectively compensate for the intrinsic electron deficiency of boron and lead to interesting boron-based binary clusters, owing to the small electronegativity of the former elements. We report on the computational design of a three-layered sandwich cluster, Na(5)B(7), on the basis of global-minimum (GM) searches and electronic structure calculations. It is shown that the Na(5)B(7) cluster can be described as a charge-transfer complex: [Na(4)](2+)[B(7)](3-)[Na](+). In this sandwich cluster, the [B(7)](3-) core assumes a molecular wheel in shape and features in-plane hexagonal coordination. The magic 6π/6σ double aromaticity underlies the stability of the [B(7)](3-) molecular wheel, following the (4n + 2) Hückel rule. The tetrahedral Na(4) ligand in the sandwich has a [Na(4)](2+) charge-state, which is the simplest example of three-dimensional aromaticity, spherical aromaticity, or superatom. Its 2σ electron counting renders σ aromaticity for the ligand. Overall, the sandwich cluster has three-fold 6π/6σ/2σ aromaticity. Molecular dynamics simulation shows that the sandwich cluster is dynamically fluxional even at room temperature, with a negligible energy barrier for intramolecular twisting between the B(7) wheel and the Na(4) ligand. The Na(5)B(7) cluster offers a new example for dynamic structural fluxionality in molecular systems.