Structure and Magnetic Behavior of Layered Honeycomb Tellurates, BiM(III)TeO6 (M = Cr, Mn, Fe)

• Published in: Inorganic chemistry 2016-10, Vol.55 (20), p.10229-10237
• Main Authors: Kim, Sun Woo, Deng, Zheng, Fischer, Zachary, Lapidus, Saul H., Stephens, Peter W., Li, Man-Rong, Greenblatt, Martha
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.6b01472

New layered honeycomb tellurates, BiM­(III)­TeO6 (M = Cr, Mn, Fe) were synthesized and characterized. BiM­(III)­TeO6 (M = Cr, Fe) species crystallize in a trigonal space group, P3̅1c (No. 163), of edge-sharing M3+/Te6+O6 octahedra, which form honeycomb-like double layers in the ab plane with Bi3+ cations located between the layers. Interestingly, the structure of BiMnTeO6 is similar to those of the Cr/Fe analogues, but with monoclinic space group, P21/c (No. 14), attributed to the strong Jahn–Teller distortion of Mn3+ cations. The crystal structure of BiM­(III)­TeO6 is a superstructure of PbSb2O6-related materials (ABB′O6). The Cr3+ and Fe3+ cations are ordered 80% and 90%, respectively, while the Mn3+ ions are completely ordered on the B-site of the ABB′O6 structure. BiCrTeO6 shows a broad antiferromagnetic transition (AFM) at ∼17 K with a Weiss temperature (θ) of −59.85 K, while BiFeTeO6 and BiMnTeO6 show sharp AFM transitions at ∼11 K with θ of −27.56 K and at ∼9.5 K with θ of −17.57 K, respectively. These differences in the magnetic behavior are ascribed to the different concentration of magnetic nearest versus next-nearest neighbor interactions of magnetic cations due to the relative differences in the extent of M/Te ordering.