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Variable Dimensionality, Valence, and Magnetism in Fluoride-Rich Iron Phosphates BaxFex(PO4)F-y (1 <= x <= 3, 2 <= y <= 12)

Authors
Jiang, JianhuaLee, SuheonZhu, BeiYu, YangWaerenborgh, Joao CarlosChoi, Kwang-YongLu, 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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