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Functionalised polyhedral oligomeric silsesquioxane with encapsulated fluoride – first observation of fluxional Si⋯F interactions in POSS

Abstract : The synthesis of a styryl functionalised POSS incorporating an encapsulated fluoride ion within a (SiO1.5)8 cage (T8-F) is reported. It was characterised by single crystal XRD, MALDI-MS, FTIR, solution (29Si, 19F, 13C, 1H) and solid state (29Si, 19F) NMR. In the absence of 1H decoupling, the 29Si solution NMR spectrum exhibited a triplet of doublets. In contrast, 1H, 19F and 1H/19F double-decoupling resulted in two, three and one signal, respectively, being consistent with a single Si site whose 29Si NMR signal is modulated by both the proximal aromatic-ring protons and fluoride. The associated Si⋯F coupling constant (2.5 Hz) is substantially lower than expected for a covalent Si–F bond and arises from a fluxional Si⋯F covalent effect in which the F− interacts equivalently with all eight Si atoms. Additional variable temperature NMR studies demonstrated a threshold at −5 °C below which no Si⋯F interactions are observed, and above which an increasing Si⋯F covalent character occurs.
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https://hal.archives-ouvertes.fr/hal-03101183
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Submitted on : Thursday, January 7, 2021 - 5:06:43 AM
Last modification on : Tuesday, February 9, 2021 - 11:24:47 AM

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Dalton Trans 2021, 50, 81-89.p...
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Mathilde Laird, Cédric Totée, Philippe Gaveau, Gilles Silly, Arie van der Lee, et al.. Functionalised polyhedral oligomeric silsesquioxane with encapsulated fluoride – first observation of fluxional Si⋯F interactions in POSS. Dalton Transactions, Royal Society of Chemistry, 2021, 50 (1), pp.81-89. ⟨10.1039/d0dt03057k⟩. ⟨hal-03101183⟩

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