Variable Dimensionality, Valence, and Magnetism in Fluoride-Rich Iron Phosphates BaxFex(PO4)F-y (1 <= x <= 3, 2 <= y <= 12)
- Authors
- Jiang, Jianhua; Lee, Suheon; Zhu, Bei; Yu, Yang; Waerenborgh, Joao Carlos; Choi, Kwang-Yong; Lu, Minfeng
- Issue Date
- Jan-2019
- Publisher
- AMER CHEMICAL SOC
- Citation
- INORGANIC CHEMISTRY, v.58, no.1, pp 133 - 142
- Pages
- 10
- Journal Title
- INORGANIC CHEMISTRY
- Volume
- 58
- Number
- 1
- Start Page
- 133
- End Page
- 142
- URI
- https://scholarworks.bwise.kr/cau/handle/2019.sw.cau/18329
- DOI
- 10.1021/acs.inorgchem.8b01982
- ISSN
- 0020-1669
1520-510X
- Abstract
- We report the synthesis and characterization of three fluoride-rich barium iron phosphates BaxFex(PO4)F-y (1 <= x <= 3, 2 <= y <= 12), which exhibited abundant structural chemistry, exhibiting diverse frameworks and connecting modes between [FeOnF6-n](m-) octahedra surrounding Fe2+ or Fe3+ ions. BaFe-(PO4)F-2 (I) consisted of two-dimensional [Fe(PO4)F-2](2-) sheets built from linear (infinity)[Fe2O6F4](10-) moieties formed by fluorine corner sharing FeO4F2 and FeO2F4 octahedra with linking PO4 tetrahedra. Mixed-valence Ba2Fe2(PO4)F-6 (II) possessed a three-dimensional framework containing Fe4O6F12 tetramers formed by the edge-sharing oxygen or fluorine atoms of cis-FeF4O2 octahedra. Ba3Fe3(PO4)F-12 (III) contained one-dimensional columns of (infinity)[Fe-3(PO4)F-12](6-) infinite sections built from cis-FeF4O2 and FeF5O octahedra and tetrahedral PO4 linkers. The magnetic characterization of BaxFex(PO4)F-y unveiled diverse magnetism: an S = 5/2 spin chain for (I), a weak ferrimagnet or canted antiferromagnet for (II) thanks to the presence of distinct Fe2+ and Fe3+ sites identified by Mossbauer spectroscopy, and coupled spin-trimers for (III).
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