Boron-based ternary MgTa 2 B 6 cluster: a turning nanoclock with dynamic structural fluxionality.

Boron-based complex clusters are a fertile ground for the exploration of exotic chemical bonding and dynamic structural fluxionality. Here we report on the computational design of a ternary MgTa 2 B 6 cluster via global structural searches and quantum chemical calculations. The cluster turns out to be a new member of the molecular rotor family, closely mimicking a turning clock at the subnanoscale. It is composed of a hexagonal B 6 ring with a capping Ta atom at the top and bottom, whereas the Mg atom is linked to one Ta site as a radial Ta-Mg dimer. These components serve as the dial, axis, and hand of a nanoclock, respectively. Chemical bonding analyses reveal that the inverse sandwich Ta 2 B 6 motif in the cluster features 6π/6σ double aromaticity, whose electron counting conforms to the (4 n + 2) Hückel rule. The Ta-Mg dimer has a Lewis-type σ bond, and the Mg site has negligible bonding with B 6 ring. The ternary cluster can be formulated as an [Mg] 0 [Ta 2 B 6 ] 0 complex. Molecular dynamics simulations suggest that the cluster is structurally fluxional analogous to a nanoclock, even at a low temperature of 100 K. The Ta-Mg hand turns almost freely around the Ta 2 axis and along the B 6 dial. The tiny intramolecular rotation barrier is less than 0.3 kcal mol -1 , being dictated by the bonding nature of double 6π/6σ aromaticity. The present system offers a new type of molecular rotor in physical chemistry.