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

Taylor, Peter G., Bassindale, Alan R., El Aziz, Youssef, Pourny, Manuel, Stevenson, Richard, Hursthouse, Michael B. and Coles, Simon J. (2012) Further studies of fluoride ion entrapment in octasilsesquioxane cages; X-ray crystal structure studies and factors that affect their formation. Dalton Transactions, 41 (7), 2048-2059. (doi:10.1039/c1dt11340b).

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 sp(2) carbons, leading to a range of aryl and vinyl substituted compounds, the corresponding sp(3) 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 F-19/Si-29 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 T-8 framework and the possibility of encapsulating other anions within silsesquioxane cages have been also investigated.

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Contributors

Author: Simon J. Coles

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