Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, United Kingdom.
Inorg Chem. 2011 Aug 1;50(15):7250-6. doi: 10.1021/ic200832n. Epub 2011 Jun 29.
The low-temperature topotactic reduction of Sr(3)Fe(2-x)Co(x)O(5)Cl(2) oxychloride phases with LiH allows the preparation of phases of composition Sr(3)Fe(2-x)Co(x)O(4)Cl(2) (0 ≤ x ≤ 1). The reduced phases adopt body-centered tetragonal structures which are isostructural with Sr(3)Fe(2)O(4)Cl(2) and contain square-planar (Fe/Co)O(4) centers connected into apex-linked sheets, analogous to the CuO(2) sheets present in superconducting cuprate phases. As the cobalt concentration in Sr(3)Fe(2-x)Co(x)O(4)Cl(2) is increased the antiferromagnetic order of the Sr(3)Fe(2)O(4)Cl(2) host phase is suppressed, ultimately leading to spin-glass behavior, at low temperature, in Sr(3)Fe(2-x)Co(x)O(4)Cl(2) phases with x ≥ 0.8. The limited influence of cobalt substitution on the reactions which form the Sr(3)Fe(2-x)Co(x)O(4)Cl(2) phases is discussed and contrasted to that of the related SrFeO(3-δ)-SrFeO(2) system.
低温下，Sr(3)Fe(2-x)Co(x)O(5)Cl(2)氧氯化物与 LiH 进行拓扑还原反应，可以制备出组成式为 Sr(3)Fe(2-x)Co(x)O(4)Cl(2)（0 ≤ x ≤ 1）的相。还原相采用体心四方结构，与 Sr(3)Fe(2)O(4)Cl(2)同构，包含连接成顶点相连的片状的平面四方（Fe/Co）O(4)中心，类似于超导铜酸盐相中存在的 CuO(2)片状结构。随着 Sr(3)Fe(2-x)Co(x)O(4)Cl(2)中钴浓度的增加，Sr(3)Fe(2)O(4)Cl(2)主相的反铁磁有序被抑制，最终导致 Sr(3)Fe(2-x)Co(x)O(4)Cl(2)相在 x ≥ 0.8 时在低温下表现出自旋玻璃行为。钴取代对形成 Sr(3)Fe(2-x)Co(x)O(4)Cl(2)相的反应的影响有限，并与相关的 SrFeO(3-δ)-SrFeO(2)体系进行了讨论和对比。
