Graduate School of Engineering, Kyoto University, 615-8510, Kyoto, Japan.
Center for Neutron Research, National Institute of Standards and Technology (NIST), Gaithersburg, MD, 20899, USA.
Angew Chem Int Ed Engl. 2016 Aug 8;55(33):9667-70. doi: 10.1002/anie.201605123. Epub 2016 Jun 29.
The high-pressure synthesis of a manganese oxyhydride LaSrMnO3.3 H0.7 is reported. Neutron and X-ray Rietveld analyses showed that this compound adopts the K2 NiF4 structure with hydride ions positioned exclusively at the equatorial site. This result makes a striking contrast to topochemical reductions of LaSrMnO4 that result in only oxygen-deficient phases down to LaSrMnO3.5 . This suggests that high H2 pressure plays a key role in stabilizing the oxyhydride phase, offering an opportunity to synthesize other transition-metal oxyhydrides. Magnetic susceptibility revealed a spin-glass transition at 24 K that is due to competing ferromagnetic (Mn(2+) -Mn(3+) ) and antiferromagnetic (Mn(2+) -Mn(2) , Mn(3+) -Mn(3+) ) interactions.
报道了锰氢氧化物 LaSrMnO3.3 H0.7 的高压合成。中子和 X 射线 Rietveld 分析表明,该化合物采用 K2 NiF4 结构,氢化物离子仅位于赤道位置。这一结果与 LaSrMnO4 的拓扑化学还原形成鲜明对比,后者仅导致氧缺陷相直到 LaSrMnO3.5。这表明高 H2 压力在稳定氢氧化物相方面起着关键作用,为合成其他过渡金属氢氧化物提供了机会。磁化率显示出 24 K 处的自旋玻璃转变,这是由于竞争的铁磁(Mn(2+) -Mn(3+))和反铁磁(Mn(2+) -Mn(2+),Mn(3+) -Mn(3+))相互作用所致。