Post-synthesis modification of functionalised polyhedral oligomeric silsesquioxanes with encapsulated fluoride : enhancing reactivity of T8-F POSS for materials synthesis

Mathilde Laird, Philippe Gaveau, Philippe Trens, Carole Carcel, Masafumi Unno, John R. Bartlett, Michel Wong Chi Man

Research output: Contribution to journalArticlepeer-review

Abstract

Previous studies have demonstrated that functionalised T-8 polyhedral oligomeric silsesquioxanes with fluoride anions encapsulated within the T-8 cage (T-8-F) have very low reactivity, with no reports of successful modification of the organic moieties. Herein, we report the successful modification of a styryl functionalised T-8-F compound with mercaptopropyltriethoxysilane using a thiol-ene click reaction. This strategy enables the vinyl moiety to be modified while maintaining the influence of the electron-withdrawing phenylene group, which stabilises the fluoride within the cage. The triethoxysilylated T-8-F cages were subsequently converted into nanohybrids by sol-gel processing. Multinuclear NMR experiments (Si-29, F-19, C-13) demonstrated that the POSS cage remained intact during both post functionalisation of T-8-F and subsequent sol-gel processing. Furthermore, Si-29 cross polarisation solid state NMR experiments using F-19 as a cross polarisation agent demonstrated that the fluoride anions remain localised within the cages in the nanohybrids. The functionalisation of the styryl bearing T-8-F POSS cage is the first example of both the successful modification of the poorly reactive T-8-F family and the formation of a nanohybrid material incorporating fluoride ions immobilised within covalently bound T-8 cages.
Original languageEnglish
Pages (from-to)4227-4235
Number of pages9
JournalNew Journal of Chemistry
Volume45
Issue number9
DOIs
Publication statusPublished - 2021

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