Using 17O solid-state NMR and first principles calculation to characterise structure and dynamics in inorganic framework materials.

The use of solid-state (17)O NMR to determine local chemical environment and to characterise oxygen dynamics is illustrated in studies of zirconium tungstate, ZrW(2)O(8), and tungsten oxide, WO(3). Simple 1D magic-angle spinning (MAS) NMR allows the chemical environments in ZrW(2)O(8) to be readily characterised, and the use of a combination of one- and two-dimensional experiments to characterise oxygen dynamics in its cubic phase is reviewed. Combining local information about structure and dynamics from NMR with long-range structural information from diffraction allows a comprehensive picture of the material to be developed. Recent work is described that uses first principles calculation of NMR parameters to probe subtle asymmetries in the WO(6) octahedra that form the structural motif in WO(3). NMR is shown to be a highly sensitive probe of local structure, allowing different models derived from high-quality neutron diffraction studies to be distinguished. The density functional theory (DFT) calculations allow clear correlations between (17)O chemical shifts and distortions of the structure to be established.