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钼酸钍铷家族中的高温相变、光谱性质及降维

High-temperature phase transitions, spectroscopic properties, and dimensionality reduction in rubidium thorium molybdate family.

作者信息

Xiao Bin, Gesing Thorsten M, Kegler Philip, Modolo Giuseppe, Bosbach Dirk, Schlenz Hartmut, Suleimanov Evgeny V, Alekseev Evgeny V

机构信息

Institute for Energy and Climate Research (IEK-6), Forschungszentrum Jülich GmbH , 52428 Jülich, Germany.

出版信息

Inorg Chem. 2014 Mar 17;53(6):3088-98. doi: 10.1021/ic403003f. Epub 2014 Mar 6.

DOI:10.1021/ic403003f
PMID:24601566
Abstract

Four new rubidium thorium molybdates have been synthesized by high-temperature solid-state reactions. The crystal structures of Rb8Th(MoO4)6, Rb2Th(MoO4)3, Rb4Th(MoO4)4, and Rb4Th5(MoO4)12 were determined using single-crystal X-ray diffraction. All these compounds construct from MoO4 tetrahedra and ThO8 square antiprisms. The studied compounds adopt the whole range of possible structure dimensionalities from zero-dimensional (0D) to three-dimensional (3D): finite clusters, chains, sheets, and frameworks. Rb8Th(MoO4)6 crystallizes in 0D containing clusters of Th(MoO4)6. The crystal structure of Rb2Th(MoO4)3 is based upon one-dimensional chains with configuration units of Th(MoO4)3. Two-dimensional sheets occur in compound Rb4Th(MoO4)4, and a 3D framework with channels formed by thorium and molybdate polyhedra has been observed in Rb4Th5(MoO4)12. The Raman and IR spectroscopic properties of these compounds are reported. Temperature-depended phase transition effects were observed in Rb2Th(MoO4)3 and Rb4Th(MoO4)4 using thermogravimetry-differential scanning calorimetry analysis and high-temperature powder diffraction methods.

摘要

通过高温固态反应合成了四种新型铷钍钼酸盐。利用单晶X射线衍射测定了Rb8Th(MoO4)6、Rb2Th(MoO4)3、Rb4Th(MoO4)4和Rb4Th5(MoO4)12的晶体结构。所有这些化合物均由MoO4四面体和ThO8方形反棱柱构成。所研究的化合物呈现出从零维(0D)到三维(3D)的各种可能的结构维度:有限簇、链、层和骨架。Rb8Th(MoO4)6以包含Th(MoO4)6簇的0D形式结晶。Rb2Th(MoO4)3的晶体结构基于具有Th(MoO4)3构型单元的一维链。化合物Rb4Th(MoO4)4中出现二维层,并且在Rb4Th5(MoO4)12中观察到由钍和钼酸盐多面体形成通道的三维骨架。报道了这些化合物的拉曼光谱和红外光谱性质。使用热重-差示扫描量热分析和高温粉末衍射方法在Rb2Th(MoO4)3和Rb4Th(MoO4)4中观察到了温度依赖性相变效应。

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