On phosphorus chemical shift anisotropy in metal (IV) phosphates and phosphonates: A ³¹ P NMR experimental study

The phosphorus chemical shift anisotropies, ³¹ PΔcs, and asymmetry parameters η were measured by the ³¹ P{¹ H} NMR experiments in static and low-frequency spinning samples of the zirconium phosphates and phosphonates and also in the mixed Zr (IV)/Sn (IV) phosphate/phosphonate material. The data obtained have shown a 111 connectivity in the HPO₄ and PO₃ groups, which does not change at modification and intercalation of the materials. The ³¹ PΔcs values of the phosphonate groups (43-49 ppm) significantly surpass the values characterizing the HPO₄ groups (23-37 ppm). The ³¹ P Δcs values obtained for the metal (IV) phosphates were discussed in terms of P-O distances. The ³¹ P chemical shift anisotropy parameters can help at elucidation of local structures in phosphate and phosphonate materials.