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Open‐Shell 3d Transition Metal Nitridophosphates M II P 8 N 14 ( M II =Fe, Co, Ni) by High‐Pressure Metathesis
Author(s) -
Kloß Simon D.,
Janka Oliver,
Block Theresa,
Pöttgen Rainer,
Glaum Robert,
Schnick Wolfgang
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201809146
Subject(s) - paramagnetism , antiferromagnetism , crystallography , octahedron , chemistry , transition metal , mössbauer spectroscopy , metal , ligand field theory , nitride , ion , analytical chemistry (journal) , crystal structure , catalysis , condensed matter physics , physics , biochemistry , chromatography , organic chemistry , layer (electronics)
3d transition metal nitridophosphates M II P 8 N 14 ( M II =Fe, Co, Ni) were prepared by high‐pressure metathesis indicating that this route might give a systematic access to a structurally rich family of M ‐P‐N compounds. Their structures, which are stable in air up to at least 1273 K, were determined through powder X‐ray diffraction and consist of highly condensed tetra‐layers of PN 4 tetrahedra and M N 6 octahedra. Magnetic measurements revealed paramagnetic behavior of CoP 8 N 14 and NiP 8 N 14 down to low temperatures while, FeP 8 N 14 exhibits an antiferromagnetic transition at T N =3.5(1) K. Curie–Weiss fits of the paramagnetic regime indicate that the transition metal cations are in a oxidation state +II, which was corroborated by Mössbauer spectroscopy for FeP 8 N 14 . The ligand field exerted by the nitride ions in CoP 8 N 14 and NiP 8 N 14 was determined from UV/Vis/NIR data and is comparable to that of aqua‐ligands and oxophosphates.