Insertion of Trivalent Lanthanides into Uranyl Vanadate Layers and Frameworks.

Insertion of Trivalent Lanthanides into Uranyl Vanadate Layers and Frameworks.
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将三价镧系元素插入钒酸铀酰层和框架中。

DOI:
10.1021/acs.inorgchem.5b01141
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发表时间:
2015-08
影响因子:
4.6
通讯作者:
Wang, Shuao
Wang, Shuao
中科院分区:
化学2区
文献类型:
--
作者:
Diwu, Juan;Chai, Zhifang;Albrecht-Schmitt, Thomas E;Wang, Shuao

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通过水热反应合成了两种新的铀酰钒酸盐,并用单晶X射线衍射法对其结构进行了表征。(H3O)UO2VO4(UVO-1)的结构是由UO2(2+)五方双金字塔配位的阴离子层组成,其电荷由层间H3O(+)阳离子平衡。钒在(UO2)_3(VO_4)_2(H_2O)_3(UVO-2)中以单体VO_4四面体的形式与UO_2(2+)五方双锥配位,形成三维铀酰(VI)钒酸盐骨架。通过添加Ln(NO3)3(Ln=Nd,Eu)的类似反应,合成了三个稀土钒酸铀酰异质骨架:Nd(UO2)3(VO4)3(H2O)11(NdUVO-1),Eu(UO2)3(VO4)3(H2O)3(H2O)10(EuUVO-1)和Eu2(UO2)12(VO4)10(H2O)24(EuUVO-2)。在NdUVO-1和EuUVO-1中,Ln(3+)离子被插入到UVO-1的层间空间中,取代了H3O(+),并进一步将相邻的层桥接到3D骨架中。同样,EuUVO-2采用与UVO-2相同的片状拓扑结构,Eu(3+)离子取代了UVO-2中的一些层间铀酰离子。我们的工作表明,钒酸铀酰扩展结构是进一步掺入三价镧系元素/吖系元素阳离子的良好载体,并为合成新的异双金属4f-5f和5f-5f化合物提供了一条新的途径。
Two new uranyl vanadates have been prepared from hydrothermal reactions and structurally characterized by single-crystal X-ray diffraction. The structure of (H3O)UO2VO4 (UVO-1) consists of anionic layers containing UO2(2+) pentagonal bipyramids coordinated by edge-sharing VO5 square pyramids, with the charge balanced by interlaminar H3O(+) cations. Vanadium in (UO2)3(VO4)2(H2O)3 (UVO-2) exists as monomeric VO4 tetrahedra coordinating to UO2(2+) pentagonal bipyramids, forming a 3D uranyl(VI) vanadate framework. Similar reactions with the addition of Ln(NO3)3 (Ln = Nd, Eu) afford the three heterobimetallic lanthanide uranyl vanadate frameworks Nd(UO2)3(VO4)3(H2O)11 (NdUVO-1), Eu(UO2)3(VO4)3(H2O)10 (EuUVO-1), and Eu2(UO2)12(VO4)10(H2O)24 (EuUVO-2). In NdUVO-1 and EuUVO-1, Ln(3+) cations are inserted into the interlayer space of UVO-1 substituting for H3O(+) and further bridging adjacent layers into 3D frameworks. Similarly, EuUVO-2 adopts the same sheet topology as UVO-2, with Eu(3+) ions replacing some of the interlayer uranyl ions in UVO-2. Our work has demonstrated that uranyl vanadate extended structures are excellent hosts for further incorporation of trivalent lanthanide/actinide cations and has provided a new way to create new heterobimetallic 4f-5f and 5f-5f compounds.
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