Kim Sun Woo, Deng Zheng, Fischer Zachary, Lapidus Saul H, Stephens Peter W, Li Man-Rong, Greenblatt Martha
Department of Chemistry and Chemical Biology, Rutgers, the State University of New Jersey , 610 Taylor Road, Piscataway, New Jersey 08854, United States.
Advanced Photon Source, Argonne National Laboratory , Lemont, Illinois 60439, United States.
Inorg Chem. 2016 Oct 17;55(20):10229-10237. doi: 10.1021/acs.inorgchem.6b01472. Epub 2016 Sep 27.
New layered honeycomb tellurates, BiM(III)TeO (M = Cr, Mn, Fe) were synthesized and characterized. BiM(III)TeO (M = Cr, Fe) species crystallize in a trigonal space group, P3̅1c (No. 163), of edge-sharing M/TeO octahedra, which form honeycomb-like double layers in the ab plane with Bi cations located between the layers. Interestingly, the structure of BiMnTeO is similar to those of the Cr/Fe analogues, but with monoclinic space group, P2/c (No. 14), attributed to the strong Jahn-Teller distortion of Mn cations. The crystal structure of BiM(III)TeO is a superstructure of PbSbO-related materials (ABB'O). The Cr and Fe cations are ordered 80% and 90%, respectively, while the Mn ions are completely ordered on the B-site of the ABB'O structure. BiCrTeO shows a broad antiferromagnetic transition (AFM) at ∼17 K with a Weiss temperature (θ) of -59.85 K, while BiFeTeO and BiMnTeO 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.
合成并表征了新型层状蜂窝状碲酸盐BiM(III)TeO（M = Cr、Mn、Fe）。BiM(III)TeO（M = Cr、Fe）物种结晶于三方空间群P3̅1c（编号163），由共边的M/TeO八面体组成，这些八面体在ab平面形成蜂窝状双层结构，Bi阳离子位于层间。有趣的是，BiMnTeO的结构与Cr/Fe类似物的结构相似，但属于单斜空间群P2/c（编号14），这归因于Mn阳离子强烈的 Jahn-Teller 畸变。BiM(III)TeO的晶体结构是与PbSbO相关材料（ABB'O）的超结构。Cr和Fe阳离子的有序度分别为80%和90%，而Mn离子在ABB'O结构的B位完全有序。BiCrTeO在约17 K处显示出宽泛的反铁磁转变（AFM），魏斯温度（θ）为 -59.85 K，而BiFeTeO和BiMnTeO分别在约11 K处显示出尖锐的AFM转变，θ为 -27.56 K，在约9.5 K处显示出尖锐的AFM转变，θ为 -17.57 K。这些磁行为的差异归因于由于M/Te有序程度的相对差异，磁性阳离子的磁性最近邻与次近邻相互作用的不同浓度。
