[Cl@Si₂₀H₂₀]⁻: Parent Siladodecahedrane with Endohedral Chloride Ion

Fullerenes and diamondoids are at the core of nanoscience. Comparable monodisperse silicon analogues are scarce. Herein, we report the synthesis of the parent siladodecahedrane, which represents the largest Platonic solid. It shares its pattern of pentagonal faces with the smallest fullerene, C₂₀, and its saturated, H-terminated skeleton with diamondoids. Similar to endofullerenes, the silicon cage encapsulates a chloride ion ([Cl@Si₂₀H₂₀]⁻); similar to diamondoids, its Si–H termini offer a wealth of opportunities for further functionalization. Mere treatment with chloromethanes leads to the perchlorinated cluster [Cl@Si₂₀Cl₂₀]⁻. Both compounds were characterized by mass spectrometry, X-ray crystallography, NMR spectroscopy, and quantum-chemical calculations. The experimentally determined ³⁵Cl resonances of the endohedral chloride ions are particularly diagnostic to probe the Cl^– → Si₂₀ interaction strength as a function of the different surface substituents, as we have proven by high-level computational analyses.