Noble gas encapsulated B40 cage

Abstract

The efficacy of B₄₀ borospherene to act as a host for noble gas atoms is explored via density functional theory based computations. Although the Ng@B₄₀ complexes are thermochemically unstable with respect to dissociation into free Ng and B₄₀, it does not rule out their viability as all the systems possess a high activation free energy barrier (84.7–206.3 kcal mol⁻¹). Therefore, once they are formed, it is hard to take out the Ng atom. Two Ng atoms can also be incorporated within B₄₀ for the lighter Ng atoms (He and Ne). In fact, the destabilization offered by the encapsulation of one and two He atoms and one Ne atom inside B₄₀ is significantly less than that in experimentally synthesized He@C₂₀H₂₀, highlighting their greater possibility for synthesis. Although Ar₂ and Kr₂ encapsulated B₄₀ systems are very much destabilized by the repulsive interaction between Ng₂ and B₄₀, an inspection of the bonding situation reveals that the confinement can even induce some degree of covalent interaction between two otherwise non-bonded Ng atoms. Ng atoms transfer electrons towards B₄₀ which is smaller for lighter Ng atoms and gradually increases along He to Rn. Even if the electrostatic interaction between Ng and B₄₀ is the most predominant term in these systems, the extent of the orbital interaction is also considerable. However, the very large Pauli repulsion counterbalances the attractive interaction, eventually turning the interaction repulsive in nature. Ng@B₄₀ also shows dynamical behaviour involving continuous exchange between hexagonal and heptagonal holes, similar to the host cage, as understood from the very little variation in the activation barrier because of the Ng encapsulation. Furthermore, sandwich complexes like [(η⁵-C₅Me₅)Fe(η⁶-B₄₀)]⁺ and [(η⁵-C₅Me₅)Fe(η⁷-B₄₀)]⁺ are noted to be viable with the latter being slightly more stable than the former. The encapsulation of Xe slightly improves the dissociation energy associated with the decomposition into Xe@B₄₀ and [Fe(η⁵-C₅Me₅)]⁺ compared to that in the bare one.