Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, United Kingdom.
J Am Chem Soc. 2013 Feb 6;135(5):1838-44. doi: 10.1021/ja309798e. Epub 2013 Jan 28.
Low-temperature topochemical reduction of the cation disordered perovskite phase SrFe(0.5)Ru(0.5)O(3) with CaH(2) yields the infinite layer phase SrFe(0.5)Ru(0.5)O(2). Thermogravimetric and X-ray absorption data confirm the transition metal oxidation states as SrFe(0.5)(2+)Ru(0.5)(2+)O(2); thus, the title phase is the first reported observation of Ru(2+) centers in an extended oxide phase. DFT calculations reveal that, while the square-planar Fe(2+) centers adopt a high-spin S = 2 electronic configuration, the square-planar Ru(2+) cations have an intermediate S = 1 configuration. This combination of S = 2, Fe(2+) and S = 1, Ru(2+) is consistent with the observed spin-glass magnetic behavior of SrFe(0.5)Ru(0.5)O(2).
用 CaH2 对阳离子无序钙钛矿相 SrFe(0.5)Ru(0.5)O3 进行低温拓扑化学反应，生成无限层相 SrFe(0.5)Ru(0.5)O2。热重分析和 X 射线吸收数据证实过渡金属的氧化态为 SrFe(0.5)(2+)Ru(0.5)(2+)O2；因此，标题相是首次在扩展氧化物相中观察到 Ru(2+)中心。密度泛函理论计算表明，虽然平面四方 Fe(2+)中心采用高自旋 S = 2 电子构型，但平面四方 Ru(2+)阳离子具有中间 S = 1 构型。这种 S = 2、Fe(2+)和 S = 1、Ru(2+)的组合与 SrFe(0.5)Ru(0.5)O2 观察到的自旋玻璃磁行为一致。
