Chemical Bonding and Dynamic Structural Fluxionality of a Boron-Based Na 5 B 7 Sandwich Cluster

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 B , on the basis of global-minimum (GM) searches and electronic structure calculations. It is shown that the Na B cluster can be described as a charge-transfer complex: [Na ] [B ] [Na] . In this sandwich cluster, the [B ] 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 ] molecular wheel, following the (4 + 2) Hückel rule. The tetrahedral Na ligand in the sandwich has a [Na ] 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 wheel and the Na ligand. The Na B cluster offers a new example for dynamic structural fluxionality in molecular systems.