Layered oxychlorides [PbBiO2]An+1BnO3n-1Cl2 (A = Pb/Bi, B = Fe/Ti): Intergrowth of the hematophanite and sillen phases

Maria Batuk, Dmitry Batuk, Alexander A. Tsirlin, Dmitry S. Filimonov, Denis V. Sheptyakov, Matthias Frontzek, Joke Hadermann, Artem M. Abakumov

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13 Citations (Scopus)

Abstract

New layered structures corresponding to the general formula [PbBiO2]An+1BnO3n-1Cl2 were prepared. Pb5BiFe3O10Cl2 (n = 3) and Pb5Bi2Fe4O13Cl2 (n = 4) are built as a stacking of truncated An+1BnO3n-1 perovskite blocks and α-PbO-type [A2O2]2+ (A = Pb, Bi) blocks combined with chlorine sheets. The alternation of these structural blocks can be represented as an intergrowth between the hematophanite and Sillen-type structural blocks. The crystal and magnetic structures of Pb5BiFe3O10Cl2 and Pb5Bi2Fe4O13Cl2 were investigated in the temperature range of 1.5-700 K using X-ray and neutron powder diffraction, transmission electron microscopy and 57Fe Mössbauer spectroscopy. Both compounds crystallize in the I4/mmm space group with the unit cell parameters a ≈ ap ≈ 3.92 Å (a unit-cell parameter of the perovskite structure), c ≈ 43.0 Å for the n = 3 member and c ≈ 53.5 Å for the n = 4 member. Despite the large separation between the slabs containing the Fe3+ ions (nearly 14 Å), long-range antiferromagnetic order sets in below ∼600 K with the G-type arrangement of the Fe magnetic moments aligned along the c-axis. The possibility of mixing d0 and dn cations at the B sublattice of these structures was also demonstrated by preparing the Ti-substituted n = 4 member Pb6BiFe3TiO13Cl2.

Original languageEnglish
Pages (from-to)2946-2956
Number of pages11
JournalChemistry of Materials
Volume27
Issue number8
DOIs
Publication statusPublished - 28 Apr 2015
Externally publishedYes

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