Open-Shell 3d Transition Metal Nitridophosphates (MP8N14)-P-II (M-II = Fe, Co, Ni) by High-Pressure Metathesis

Kloss, Simon D.; Janka, Oliver; Block, Theresa; Poettgen, Rainer; Glaum, Robert und Schnick, Wolfgang (2019): Open-Shell 3d Transition Metal Nitridophosphates (MP8N14)-P-II (M-II = Fe, Co, Ni) by High-Pressure Metathesis. In: Angewandte Chemie-International Edition, Vol. 58, No. 14: pp. 4685-4689

Abstract

3d transition metal nitridophosphates (MP8N14)-P-II (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 1273K, were determined through powder X-ray diffraction and consist of highly condensed tetra-layers of PN4 tetrahedra and MN6 octahedra. Magnetic measurements revealed paramagnetic behavior of CoP8N14 and NiP8N14 down to low temperatures while, FeP8N14 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 Mossbauer spectroscopy for FeP8N14. The ligand field exerted by the nitride ions in CoP8N14 and NiP8N14 was determined from UV/Vis/NIR data and is comparable to that of aqua-ligands and oxophosphates.

• Item Type: Journal article
• Faculties: Chemistry and Pharmacy > Department of Chemistry
• Subjects: 500 Science > 540 Chemistry
• ISSN: 1433-7851
• Language: English