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 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 (4 n + 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.