Phase-pure polycrystalline BaRuMnO was prepared and determined to adopt the noncentrosymmetric polar crystal structure (space group 2) based on results of second harmonic generation, convergent beam electron diffraction, and Rietveld refinements using powder neutron diffraction data. The crystal structure features zigzag chains of corner-shared trimers, which contain three distorted face-sharing octahedra. The three metal sites in the trimers are occupied by disordered Ru/Mn with three different ratios: Ru1:Mn1 = 0.202(8):0.798(8), Ru2:Mn2 = 0.27(1):0.73(1), and Ru3:Mn3 = 0.40(1):0.60(1), successfully lowering the symmetry and inducing the polar crystal structure from the centrosymmetric parent compounds BaTO (T = Mn, Ru; space group ). The valence state of Ru/Mn is confirmed to be +4 according to X-ray absorption near-edge spectroscopy. BaRuMnO is a narrow bandgap (∼0.6 eV) semiconductor exhibiting spin-glass behavior with strong magnetic frustration and antiferromagnetic interactions.
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| http://dx.doi.org/10.1021/acs.chemmater.4c00586 | DOI Listing |
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