Phosphorus-31 solid-state nuclear magnetic resonance study of monophosphazenes

Simultaneous observation of anisotropic chemical shielding and dipolar coupling in polycrystalline monophosphazenes has been used to obtain information on the 31P–14N spin pair. Phosphorus-31 chemical shielding tensor components have been determined; the most shielded component was found to lie along the P=N bond. The 31P–14N dipolar coupling constants have provided P=N bond lengths from powder samples, equivalent for all compounds within experimental error; the value obtained for N–(triphenylphosphoranylidene)-aniline is in excellent agreement with that obtained in a recent X-ray diffraction study. Features of crystallographic significance have been determined from the solid-state nuclear magnetic resonance spectra for two of the compounds without resorting to diffraction techniques. Information on the magnitude and orientation of the 14N electric field gradient tensor has been inferred from 31P MAS spectra and abinitio calculations. Keywords: monophosphazenes, dipolar nmr, 31P chemical shielding anisotropies, solid-state nmr.