Cl@Si₂₀X₂₀ cages: Evaluation of encapsulation nature, structural rigidity, and ²⁹Si-NMR patterns using relativistic DFT calculations

The experimental characterization of Cl@Si₂₀ endohedral clusters, featuring different ligands such as [Cl@Si₂₀H₂₀]⁻ (1) [Cl@Si₂₀H₁₂Cl₈]⁻ (2), and [Cl@Si₂₀Cl₂₀]⁻ (3), provides insight into the variable encapsulation environment for chloride anions. The favorable formation of such species enables the evaluation of the encapsulation nature and the role of the inner anion in the rigidity of the overall cluster. Our results show a sizable interaction which increases as −66.7, −100.8, and −130.3 kcal mol⁻¹ from 1 to 3, respectively, featuring electrostatic character. The orbital interaction involves 3p-Cl → Si₂₀X₂₀ and 3s-Cl → Si₂₀X₂₀ charge transfer channels and a slight contribution from London dispersion-type interactions. These results show that the inner bonding environment can be modified by the choice of exobonded ligands. Moreover, ²⁹Si-NMR parameters are depicted in terms of the chemical shift anisotropy (CSA), leading to a strong variation of the three principal tensor components (δ₁₁, δ₂₂, δ₃₃), unraveling the origin of the experimental ²⁹Si-NMR chemical shift (δ_iso) differences along the given series. Thus, the Si₂₀ cage is a useful template to further evaluate different environments for encapsulating atomic species.