Xiao Bin, Gesing Thorsten M, Kegler Philip, Modolo Giuseppe, Bosbach Dirk, Schlenz Hartmut, Suleimanov Evgeny V, Alekseev Evgeny V
Institute for Energy and Climate Research (IEK-6), Forschungszentrum Jülich GmbH , 52428 Jülich, Germany.
Inorg Chem. 2014 Mar 17;53(6):3088-98. doi: 10.1021/ic403003f. Epub 2014 Mar 6.
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.
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。