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  • Title: Two new noncentrosymmetric (NCS) polar oxides: syntheses, characterization, and structure-property relationships in BaMTe2O7 (M = Mg2+ or Zn2+).
    Author: Yeon J, Kim SH, Nguyen SD, Lee H, Halasyamani PS.
    Journal: Inorg Chem; 2012 Feb 20; 51(4):2662-8. PubMed ID: 22296559.
    Abstract:
    Two new noncentrosymmetric (NCS) polar oxides, BaMgTe(2)O(7) and BaZnTe(2)O(7), have been synthesized and characterized, with their crystal structures determined by single crystal X-ray diffraction. The iso-structural materials exhibit structures consisting of layers of corner-shared MgO(5) or ZnO(5), Te(6+)O(6), and Te(4+)O(4) polyhedra that are separated by Ba(2+) cations. The Te(4+) cation is found in a highly asymmetric and polar coordination environment attributable to its stereoactive lone-pair. The alignment of the individual TeO(4) polar polyhedra results in macroscopic polarity for BaMgTe(2)O(7) and BaZnTe(2)O(7). Powder second-harmonic generation (SHG) measurements revealed a moderate SHG efficiency of approximately 5 × KDP (or 200 × α-SiO(2)) for both materials. Piezoelectric charge constants of 70 and 57 pm/V, and pyroelectric coefficients of -18 and -10 μC·m(-2)·K(-1) were obtained for BaMgTe(2)O(7) and BaZnTe(2)O(7), respectively. Although the materials are polar, frequency dependent polarization measurements indicated that the materials are not ferroelectric, that is, the observed macroscopic polarization cannot be reversed. Infrared, UV-vis diffuse spectroscopy, and thermal properties were also measured. Crystal data: BaMgTe(2)O(7), orthorhombic, space group Ama2 (No. 40), a = 5.558(2) Å, b = 15.215(6) Å, c = 7.307(3) Å, V = 617.9(4) Å(3), and Z = 4; BaZnTe(2)O(7), orthorhombic, space group Ama2 (No. 40), a = 5.5498(4) Å, b = 15.3161(11) Å, c = 7.3098(5) Å, V = 621.34(8) Å(3), and Z = 4.
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