Preparation, Crystal Chemistry, and Hidden Magnetic Order in the Family of Trigonal Layered Tellurates A2Mn(4+)TeO6 (A = Li, Na, Ag, or Tl)

Vladimir B Nalbandyan; Igor L Shukaev; Grigory V Raganyan; Artem Svyazhin; Alexander N Vasiliev; Elena A Zvereva

doi:10.1021/acs.inorgchem.8b03445

Preparation, Crystal Chemistry, and Hidden Magnetic Order in the Family of Trigonal Layered Tellurates A₂Mn(4+)TeO₆ (A = Li, Na, Ag, or Tl)

Inorg Chem. 2019 May 6;58(9):5524-5532. doi: 10.1021/acs.inorgchem.8b03445. Epub 2019 Apr 17.

Authors

Vladimir B Nalbandyan¹, Igor L Shukaev¹, Grigory V Raganyan², Artem Svyazhin^{3

4}, Alexander N Vasiliev^{2

5

6}, Elena A Zvereva^{2

5}

Affiliations

¹ Chemistry Faculty , Southern Federal University , Rostov-on-Don 344090 , Russia.
² Physics Faculty , M. V. Lomonosov Moscow State University , Moscow 119991 , Russia.
³ European Synchrotron Radiation Facility , Grenoble 38043 , France.
⁴ M. N. Mikheev Institute of Metal Physics of Ural Branch of Russian Academy of Sciences , Yekaterinburg 620990 , Russia.
⁵ National Research South Ural State University , Chelyabinsk 454080 , Russia.
⁶ National University of Science and Technology "MISiS" , Moscow 119049 , Russia.

PMID: 30995026
DOI: 10.1021/acs.inorgchem.8b03445

Abstract

We report the first four magnetic representatives of the trigonal layered A₂M(4+)TeO₆ (here, M = Mn) family. Na₂MnTeO₆ was synthesized from NaMnO₂, NaNO₃, and TeO₂ at 650-720 °C, but analogues for which A = Li and K could not be obtained by direct synthesis. However, those for which A = Li, Ag, and Tl (but not K) were prepared by exchange reactions between Na₂MnTeO₆ and the corresponding molten nitrates. The oxygen content was verified by redox titration. According to the X-ray diffraction Rietveld analysis, the four new compounds are isostructural with Na₂GeTeO₆, trigonal ( P3̅1 c), based on ilmenite-like layers of edge-shared oxygen octahedra occupied by Mn(4+) and Te(6+) in an ordered manner. These layers are separated by cations A, also in a distorted octahedral coordination. However, off-center displacement of Tl⁺ is so strong, due to the lone-pair effect, that its coordination is better described as trigonal pyramid. Each MnO₆ octahedron shares two opposite faces with AO₆ octahedra, whereas TeO₆ octahedra avoid sharing faces. Besides this double-layered structure, Na₂MnTeO₆ was often accompanied by a transient triple-layered rhombohedral polytype. However, it could not be prepared as a single phase and disappeared on annealing at 700-720 °C. All A₂MnTeO₆ samples (A = Ag, Li, Na, or Tl) revealed the unusual phenomenon of hidden magnetic order. Low-field magnetic susceptibility data exhibit a Curie-Weiss type behavior for all samples under study and do not show any sign of the establishment of long-range magnetic order down to 2 K. In contrast, both the magnetic susceptibility in sufficiently high external magnetic fields and the zero-field specific heat unambiguously revealed an onset of antiferromagnetic order at low temperatures. The frustration index f = Θ/ T_N takes values larger than the classical values for three-dimensional antiferromagnets and implies moderate frustration on the triangular lattice.