Instituto de Ciencia de Materiales de Madrid, C.S.I.C., Cantoblanco E-28049, Madrid, Spain.
Dalton Trans. 2012 Jul 28;41(28):8575-84. doi: 10.1039/c2dt30350g. Epub 2012 Jun 6.
The members of the family of pyrochlore oxides with the formula R(2)MnRuO(7) (R = Tb, Dy, Ho, Er, Tm, Yb, Lu and Y) have been synthesized and characterized. Polycrystalline samples were prepared by a soft chemistry procedure involving citrates of the different metal ions, followed by thermal treatments in air or O(2) pressure. The crystallographic and magnetic structures have been analysed from X-ray diffraction (XRD) and neutron powder diffraction (NPD) data, in complement with magnetic measurements; the evolution along the series of the crystallographic parameters (unit-cell parameters, bond distances and angles) is discussed. In R(2)MnRuO(7) pyrochlores, Mn and Ru ions statistically occupy the 16c sites in a cubic unit cell with space group Fd ̅3m, which defines an intrinsic frustrated three-dimensional system. In all the cases, the low-temperature NPD data unveils an antiferromagnetic coupling of two subsets of Mn(4+)/Ru(4+) spins, indicating that the magnetic frustration is partially relieved by the random distribution of Mn and Ru over the 16c sites. At lower temperatures there is a polarization of the R(3+) magnetic moments, which also participate in the magnetic structure, when a magnetic rare earth is present.
具有通式 R(2)MnRuO(7)(R = Tb、Dy、Ho、Er、Tm、Yb、Lu 和 Y)的烧绿石氧化物家族成员已经被合成并进行了表征。多晶样品是通过涉及不同金属离子的柠檬酸盐的软化学程序,然后在空气或 O(2)压力下进行热处理制备的。晶体和磁结构已经从 X 射线衍射 (XRD) 和中子粉末衍射 (NPD) 数据进行了分析,并用磁测量进行了补充;讨论了沿系列的晶体学参数(晶胞参数、键长和角度)的演变。在 R(2)MnRuO(7)烧绿石中,Mn 和 Ru 离子在具有空间群 Fd ̅3m 的立方晶胞中统计占据 16c 位,这定义了一个内在的受挫三维系统。在所有情况下,低温 NPD 数据揭示了 Mn(4+)/Ru(4+)自旋的两个子集的反铁磁耦合,表明 Mn 和 Ru 在 16c 位上的随机分布部分缓解了磁受挫。在较低温度下,当存在磁性稀土时,R(3+)磁矩发生极化,这也参与了磁结构。