Mutschke Alexander, Schulz Annika, Bertmer Marko, Ritter Clemens, Karttunen Antti J, Kieslich Gregor, Kunkel Nathalie
Chair of Inorganic Chemistry with Focus on Novel Materials, Technical University of Munich Lichtenbergstrasse 4 85748 Garching Germany
Felix Bloch Institute for Solid State Physics Leipzig University Linnéstrasse 5 04103 Leipzig Germany.
Chem Sci. 2022 May 25;13(26):7773-7779. doi: 10.1039/d2sc01861f. eCollection 2022 Jul 6.
The four compounds AMOH (A = Rb, Cs; M = Mo, W) are introduced as the first members of the new material class of the transition oxometalate hydrides. The compounds are accessible a thermal synthesis route with carefully controlled conditions. Their crystal structures were solved by neutron diffraction of the deuterated analogues. RbMoOD, CsMoOD and CsWOD crystallize in the antiperovskite-like KSOF-structure type, while RbWOD adopts a different orthorhombic structure. H MAS NMR, Raman spectroscopy and elemental analysis prove the abundance of hydride ions next to oxometalate ions and experimental findings are supported by quantum chemical calculations. The tetragonal phases are direct and wide band gap semiconductors arising from hydride states, whereas RbWOH shows a unique, peculiar valence band structure dominated by hydride states.
四种化合物AMOH（A = Rb、Cs；M = Mo、W）作为过渡金属氧氢化物这一新材料类别的首批成员被引入。这些化合物可通过条件严格控制的热合成路线制得。它们的晶体结构通过氘代类似物的中子衍射得以解析。RbMoOD、CsMoOD和CsWOD以类反钙钛矿KSOF结构类型结晶，而RbWOD采用不同的正交结构。固体高分辨核磁共振氢谱、拉曼光谱和元素分析证明了在金属氧离子旁边存在大量氢负离子，并且量子化学计算支持了实验结果。四方相是由氢化物态产生的直接宽带隙半导体，而RbWOH显示出由氢化物态主导的独特、奇特的价带结构。
