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La4Cu(3 - x)Zn(x)MoO12:具有 Kagomé 晶格的锌掺杂铜酸盐。

La4Cu(3-x)Zn(x)MoO12: zinc-doped cuprates with Kagomé lattices.

作者信息

Li Guobao, You Liping, Wei Wutao, Lu Yue, Ju Jing, Wannberg Anders, Rundlöf Håkan, Zou Xiaodong, Yang Tao, Tian Shujian, Liao Fuhui, Toyota Naoki, Lin Jianhua

机构信息

State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, PR China.

出版信息

J Am Chem Soc. 2005 Oct 12;127(40):14094-9. doi: 10.1021/ja053489a.

Abstract

Two solid solutions, La4Cu(3-x)Zn(x)MoO12 (0.05 < or = x < or = 0.20, SS1) and La4Cu(3-x)Zn(x)MoO12 (0.30 < or = x < or = 2.40, SS2), were synthesized at ambient pressure and at temperatures from 1025 to 1200 degrees C by traditional solid-state reactions. Their structures were determined from X-ray powder diffraction with the help of electron and neutron diffraction. The atomic arrangements of SS1 and SS2 are similar, but their space groups are different, Pmnm for SS1 and P-1 for SS2, respectively. The copper, zinc, and molybdenum are coordinated by oxygen in corner-sharing trigonal bipyramids that are sandwiched between layers of lanthanum cations. In the transition metal cations layer of SS2, the copper and zinc cations order into a Kagomé-like lattice of triangular clusters. The magnetism has been measured from 2 to 300 K and is highly influenced by the geometric arrangement of the Cu(II) and Zn(II) cations. The number of free electrons per three Cu atoms is close to one for all samples in SS1 and SS2 indicating that the system can be well expressed by independent Cu(II)3 clusters. Spontaneous magnetization was observed in the system.

摘要

通过传统的固态反应,在常压和1025至1200摄氏度的温度下合成了两种固溶体,即La4Cu(3 - x)Zn(x)MoO12(0.05≤x≤0.20,SS1)和La4Cu(3 - x)Zn(x)MoO12(0.30≤x≤2.40,SS2)。借助电子和中子衍射,通过X射线粉末衍射确定了它们的结构。SS1和SS2的原子排列相似,但它们的空间群不同,SS1为Pmnm,SS2为P - 1。铜、锌和钼由氧配位,形成角共享三角双锥,夹在镧阳离子层之间。在SS2的过渡金属阳离子层中,铜和锌阳离子排列成类似Kagomé的三角形簇晶格。在2至300 K范围内测量了磁性,其受到Cu(II)和Zn(II)阳离子几何排列的高度影响。对于SS1和SS2中的所有样品,每三个铜原子的自由电子数接近一个,这表明该体系可以用独立的Cu(II)3簇很好地表示。在该体系中观察到了自发磁化。

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