Investigation of fluorine octahedron connectivities in transition metal fluoride glasses by solid-state F-19 magic-angle-spinning nuclear magnetic resonance spectroscopy

High-resolution magic-angle-spinning (MAS) F-19 NMR spectroscopy is used to investigate the structural properties of some transition metal fluoride glasses (PbF2-ZnF2-GaF3) related to the fluorine network. Several glass compositions are investigated in order to vary the PbF2/ZnF2/GaF3 ratios. F-19 MAS NMR experiments are carried out on certain crystalline compounds selected as being the initial constituents (PbF2ZnF2,GaF3) or recrystallization compounds (Pb2ZnF6, PbGaF5, Pb3Ga2F12, Pb9Ga2F24) of glassy phases, or because they have some specific particular connectivities of the fluorine octahedron network (e.g. CsZnGaF6). It is shown that three types of fluorine are involved in the glass network: free fluorines which are not connected to transition metal ions, and shared and unshared fluorines belonging to (ZnF6)(4-) and (GaF6)(3-) octahedra. Quantitative information on these three different fluorine sites, their relative ratios in the glassy networks, and the degree of cross-linking of the fluorine octahedra is obtained. Our results prove the validity of the previously adopted assumption according to which the glass network is built up from corner-sharing fluorine octahedra centred on transition metal ions.