Morphotropy and temperature-driven polymorphism in A2Th(AsO4)2 (A = Li, Na, K, Rb, Cs) series.
Morphotropy and temperature-driven polymorphism in A2Th(AsO4)2 (A = Li, Na, K, Rb, Cs) series.
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A2Th(AsO4)2 (A = Li、Na、K、Rb、Cs) 系列中的形变性和温度驱动的多态性
DOI：
10.1021/ic5018246
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发表时间：
2014
影响因子：
4.6
通讯作者：
E. V. Alekseev
中科院分区：
文献类型：
--
作者：
V. V. Klepov;D. Bosbach;E. V. Suleimanov;Th. M. Gesing;L. Robben;E. V. Alekseev
合成并系统研究了一种新的碱式砷酸钍系列化合物。用单晶X射线衍射法测定了A_2Th(AsO_4)_2(A=Li，Na，K，Rb，Cs)的结构。Li2Th(AsO4)2和同结构的K2Th(AsO4)2和Rb2Th(AsO4)2均为单斜晶系。Na_2Th(AsO_4)_2和Cs_2Th(AsO_4)_2分别为正交晶系和四方晶系。Li2Th(AsO4)2由[Th(AsO4)2]2层组成，Li原子位于层间空间。其余的化合物是基于3D框架的。描述了与对称性有关的ThO8配位多面体局部环境的差异。尽管ThO8配位多面体的局部环境不同，结构对称性也不同，但A2Th(AsO4)2(A=Na，K，Rb，Cs)的基本网络是相同的。测量了单晶和粉末的拉曼光谱，并对谱带进行了指认。用高温粉末X射线衍射仪研究了K2Th(AsO4)2和Rb2Th(AsO4)2的DSC相变。高温X射线衍射谱表明，K_2Th(AsO_4)_2发生了两次高温多晶型转变，而Rb_2Th(AsO_4)_2只发生了一次转变。K相和Rb相的相变是可逆的。
A new alkaline thorium arsenate family was obtained and systematically investigated. The structures of A2Th(AsO4)2(A = Li, Na, K, Rb, Cs) were determined from single crystal X-ray diffraction data. Li2Th(AsO4)2and either isostructural K2Th(AsO4)2and Rb2Th(AsO4)2crystallize in the monoclinic crystal system. Na2Th(AsO4)2and Cs2Th(AsO4)2crystallize in the orthorhombic and tetragonal crystal systems, respectively. Li2Th(AsO4)2consists of [Th(AsO4)2]2–layers with Li atoms in the interlayer space. The rest of the compounds are based on 3D frameworks. Differences in local environments of ThO8coordination polyhedra are described in relation to the symmetry. Despite different local environments of ThO8coordination polyhedra and different structural symmetry, underlying nets of A2Th(AsO4)2(A = Na, K, Rb, Cs) were shown to be the same. Single-crystal and powder Raman spectra were measured, and bands are assigned. DSC measurements showed phase transitions in K2Th(AsO4)2and Rb2Th(AsO4)2, which were studied using high-temperature powder X-ray diffraction (HT-PXRD). The data of HT-PXRD demonstrates two high-temperature polymorphic modification of K2Th(AsO4)2and only one for the isotypic Rb2Th(AsO4)2. The phase transitions in both K and Rb phases are reversible.
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