Synthesis and characterisation of the quaternary nitride-fluoride Ce2MnN3F2-δ

Headspith, David A.; Sullivan, Eirin; Greaves, Colin; Francesconi, M. Grazia

Abstract

Ce 2 MnN 3 F 2-δ has been synthesised via low-temperature fluorination of the ternary nitride Ce 2 MnN 3 . To the best of our knowledge, Ce 2 MnN 3 F 2-δ is the first quaternary nitride-fluoride to be reported. The reaction of Ce 2 MnN 3 with 10% F 2 /N 2 at 95-115 °C yields the fluorinated phase Ce 2 MnN 3 F 2-δ , with tetragonal symmetry (P4/nmm a = 3.8554(4) Å and c = 13.088(4) Å based on neutron powder diffraction), accompanied by starting material. Rietveld refinement supports a staged fluorine insertion reaction (into alternate rocksalt layers) to give a product with stoichiometry Ce 2 MnN 3 F 2-δ . A comparison with the formation of Sr 2 TiO 3 F 2 and the isostructural LaSrMnO 4 F indicates that two F - anions are inserted but no F - /N 3- substitution takes place. Magnetic susceptibility measurements show a transition from Pauli paramagnetic behaviour, in Ce 2 MnN 3 , to paramagnetic behaviour upon fluorination. The effective magnetic moment in Ce 2 MnN 3 F 2-δ , μ eff = 5.38 μ B , is consistent with an intermediate value between that of Mn 3+ (4.9 μ B ) and Mn 2+ (5.9 μ B ) supporting the proposed stoichiometry, Ce 2 MnN 3 F 2-δ . © 2009 The Royal Society of Chemistry.

Citation

Headspith, D. A., Sullivan, E., Greaves, C., & Francesconi, M. G. (2009). Synthesis and characterisation of the quaternary nitride-fluoride Ce2MnN3F2-δ. Dalton Transactions : an international journal of inorganic chemistry, 9273-9279. https://doi.org/10.1039/b908591b

• Journal Article Type: Article
• Acceptance Date: Aug 19, 2009
• Online Publication Date: Sep 4, 2009
• Publication Date: Oct 27, 2009
• Deposit Date: Nov 13, 2014
• Journal: Dalton Transactions
• Print ISSN: 1477-9226
• Electronic ISSN: 1477-9234
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Issue: 42
• Pages: 9273-9279
• DOI: https://doi.org/10.1039/b908591b
• Keywords: nitride-fluorides, neutron diffraction, inorganic materials,
• Public URL: https://hull-repository.worktribe.com/output/473011
• Publisher URL: http://pubs.rsc.org/en/Content/ArticleLanding/2009/DT/b908591b#!divAbstract
• Contract Date: Nov 23, 2017