From crystalline to glassy gallium fluoride materials: an NMR study of 69Ga and 71Ga quadrupolar nuclei

Owing to the implementation of acquisition techniques specific for nuclei with very large quadrupolar interaction (full shifted echo and variable offset cumulative spectra (VOCS)), NMR spectra of 69Ga and 71Ga are obtained in crystallised (PbGaF5, Pb3Ga2F12, Pb9Ga2F24 and CsZnGaF6) and glassy (PbF2-ZnF2-GaF3) gallium fluorides. Simulations of both static (full echo or VOCS) and 15 kHz MAS spectra allow to obtain consistent determinations of isotropic chemical shifts and very large quadrupolar parameters (nuQ up to 14 MHz). In the crystalline compounds whose structures are unknown, the number and the local symmetry of the different gallium sites are tentatively worked out. For the glassy systems, a continuous Czjzek's distribution of the NMR quadrupolar parameters accounts for the particular shape of the NMR spectrum.