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Published on: September 18, 2013
Variable Dimensionality, Valence, and Magnetism in Fluoride-Rich Iron Phosphates Ba xFe x(PO4)F y (1 ≤ x ≤ 3, 2 ≤ y ≤
Jianhua Jiang1, Suheon Lee2, Bei Zhu1
1School of Environmental & Chemical Engineering , Jiangsu University of Science and Technology , Zhenjiang 212003 , Jiangsu , China.
Abstract:
We report the synthesis and characterization of three fluoride-rich barium iron phosphates Ba xFe x(PO4)F y (1 ≤ x ≤ 3, 2 ≤ y ≤ 12), which exhibited abundant structural chemistry, exhibiting diverse frameworks and connecting modes between [FeO nF6- n] m- octahedra surrounding Fe2+ or Fe3+ ions. BaFe(PO4)F2 (I) consisted of two-dimensional [Fe(PO4)F2]2- sheets built from linear ∞[Fe2O6F4]10- moieties formed by fluorine corner-sharing FeO4F2 and FeO2F4 octahedra with linking PO4 tetrahedra. Mixed-valence Ba2Fe2(PO4)F6 (II) possessed a three-dimensional framework containing Fe4O6F12 tetramers formed by the edge-sharing oxygen or fluorine atoms of cis-FeF4O2 octahedra. Ba3Fe3(PO4)F12 (III) contained one-dimensional columns of ∞[Fe3(PO4)F12]6- infinite sections built from cis-FeF4O2 and FeF5O octahedra and tetrahedral PO4 linkers. The magnetic characterization of Ba xFe x(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 Mössbauer spectroscopy, and coupled spin-trimers for (III).
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