Further studies of fluoride ion entrapment in octasilsesquioxane cages; X-ray crystal structure studies and factors that affect their formation

Abstract

A range of fluoride-encapsulated octasilsesquioxane cage compounds have been prepared using the TBAF route. Our studies suggest that whilst it is relatively straightforward to prepare fluoride-encapsulated octasilsesquioxane cage compounds with adjacent sp² carbons, leading to a range of aryl and vinyl substituted compounds, the corresponding sp³ carbon derivatives are more capricious, requiring an electron withdrawing group that can stabilize the cage whilst not acting as a leaving group. Analysis by X-ray crystallography and solution ¹⁹F/²⁹Si NMR spectroscopy of R₈T₈@F⁻ reveal very similar environments for the encapsulated fluoride octasilsesquioxane cages. Migration of a fluoride ion from inside the cage to outside the cage without breaking the T₈ framework and the possibility of encapsulating other anions within silsesquioxane cages have been also investigated.