Graduate School of Engineering, Kyoto University, Kyoto 615-8510 (Japan); The Hakubi Center for Advanced Research, Kyoto University, Kyoto (Japan).
Angew Chem Int Ed Engl. 2014 Sep 22;53(39):10377-80. doi: 10.1002/anie.201405453. Epub 2014 Aug 12.
We report a novel oxyhydride SrCrO2H directly synthesized by a high-pressure high-temperature method. Powder neutron and synchrotron X-ray diffraction revealed that this compound adopts the ideal cubic perovskite structure (Pm3̄m) with O(2-)/H(-) disorder. Surprisingly, despite the non-bonding nature between Cr 3d t(2g) orbitals and the H 1s orbital, it exhibits G-type spin ordering at T(N)≈380 K, which is higher than that of RCrO3 (R=rare earth) and any chromium oxides. The enhanced T(N) in SrCrO2H with four Cr-O-Cr bonds in comparison with RCr(3+)O3 with six Cr-O-Cr bonds is reasonably explained by the tolerance factor. The present result offers an effective strategy to tune octahedral tilting in perovskites and to improve physical and chemical properties through mixed anion chemistry.
我们报道了一种通过高温高压方法直接合成的新型氧氢化物 SrCrO2H。粉末中子和同步加速器 X 射线衍射表明,该化合物采用具有 O(2-)/H(-)无序的理想立方钙钛矿结构(Pm3̄m)。令人惊讶的是,尽管 Cr 3d(t2g)轨道和 H 1s 轨道之间没有键合性质,但它在 T(N)≈380 K 时表现出 G 型自旋有序,这高于 RCrO3(R=稀土)和任何铬氧化物。与具有六个 Cr-O-Cr 键的 RCr(3+)O3 相比,具有四个 Cr-O-Cr 键的 SrCrO2H 中 T(N) 的增强可以通过容忍因子合理地解释。该结果为通过混合阴离子化学调节钙钛矿中的八面体倾斜和改善物理化学性质提供了有效策略。