Jin Lun, Lane Michael, Zeng Dihao, Kirschner Franziska K K, Lang Franz, Manuel Pascal, Blundell Stephen J, McGrady John E, Hayward Michael A
Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, OX1 3QR, UK.
Department of Physics, Clarendon Laboratory, University of Oxford, Parks Road, OX1 3PU, UK.
Angew Chem Int Ed Engl. 2018 Apr 23;57(18):5025-5028. doi: 10.1002/anie.201800989. Epub 2018 Mar 23.
The synthesis of the first 4d transition metal oxide-hydride, LaSr NiRuO H , is prepared via topochemical anion exchange. Neutron diffraction data show that the hydride ions occupy the equatorial anion sites in the host lattice and as a result the Ru and Ni cations are located in a plane containing only hydride ligands, a unique structural feature with obvious parallels to the CuO sheets present in the superconducting cuprates. DFT calculations confirm the presence of S=1/2 Ni and S=0, Ru centers, but neutron diffraction and μSR data show no evidence for long-range magnetic order between the Ni centers down to 1.8 K. The observed weak inter-cation magnetic coupling can be attributed to poor overlap between Ni 3dz2 and H 1s in the super-exchange pathways.
首个4d过渡金属氢氧化物LaSrNiRuOH通过拓扑化学阴离子交换法合成。中子衍射数据表明，氢负离子占据主体晶格中的赤道阴离子位点，结果Ru和Ni阳离子位于仅包含氢化物配体的平面中，这是一种独特的结构特征，与超导铜酸盐中存在的CuO层有明显相似之处。密度泛函理论计算证实存在S = 1/2的Ni中心和S = 0的Ru中心，但中子衍射和μSR数据表明，直至1.8 K，Ni中心之间均未出现长程磁有序的证据。观察到的阳离子间弱磁耦合可归因于超交换途径中Ni 3dz2和H 1s之间的重叠较差。
