CeTiO₂N oxynitride perovskite: paramagnetic ¹⁴N MAS NMR without paramagnetic shifts

Abstract 14N magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of diamagnetic LaTiO2N perovskite oxynitride and its paramagnetic counterpart CeTiO2N are presented. The latter, to the best of our knowledge, constitutes the first high-resolution 14N MAS NMR spectrum collected from a paramagnetic solid material. The unpaired 4f-electrons in CeTiO2N do not induce a paramagnetic 14N NMR shift. This is remarkable given the direct Ce−N contacts in the structure for which ab initio calculations predict substantial Ce→14N contact shift interaction. The same effect is revealed with 14N MAS NMR for SrWO2N (unpaired 5d-electrons).