Post-synthesis modification of functionalised polyhedral oligomeric silsesquioxanes with encapsulated fluoride – enhancing reactivity of T 8 -F POSS for materials synthesis

• Published in: New journal of chemistry 2021-03, Vol.45 (9), p.4227-4235
• Main Authors: Laird, Mathilde, Gaveau, Philippe, Trens, Philippe, Carcel, Carole, Unno, Masafumi, Bartlett, John R., Wong Chi Man, Michel
• Format: Article
• Language: English
• Subjects: Chemical Sciences; Material chemistry
• ISSN: 1144-0546; 1369-9261
• DOI: 10.1039/D0NJ06008A

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 ( 29 Si, 19 F, 13 C) demonstrated that the POSS cage remained intact during both post functionalisation of T 8 -F and subsequent sol-gel processing. Furthermore, 29 Si cross polarisation solid state NMR experiments using 19 F 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.