Three new silver uranyl diphosphonates: structures and properties.
Three new silver uranyl diphosphonates: structures and properties.
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DOI：
10.1021/ic401897n
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发表时间：
2014-02
影响因子：
4.6
通讯作者：
Anna-Gay D. Nelson;Z. Rák;T. Albrecht‐Schmitt;U. Becker;R. Ewing
中科院分区：
文献类型：
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作者：
Anna-Gay D. Nelson;Z. Rák;T. Albrecht‐Schmitt;U. Becker;R. Ewing
在硝酸银存在下，三氧化铀与亚甲基二膦酸发生水热反应，生成了三种新的铀酰配位聚合物：AgUO 2 [CH 2（PO 3）（PO 3 H）]（Ag-1），[Ag 2（H 2 O）1. 5]{（UO 2）2[CH 2（PO 3）2] F 2}·（H 2 O）0. 5（Ag-2）和Ag 2 UO 2 [CH 2（PO 3）2]（Ag-3）.它们都由铀酰五角双锥组成，形成二维层状结构。Ag-1和Ag-3具有相同的结构单元，但结构不同; Ag-3是通过F原子的边缘共享形成UO 5 F2二聚体。pH和银阳离子对合成的结构有显著影响。Ag-1、Ag-2和Ag-3单晶的拉曼光谱分别显示了816和829、822和802 cm（-1）的v1 UO 2（2+）对称伸缩。电子结构的计算进行了使用投影增广波（PAW）方法与密度泛函理论（DFT），以深入了解合成的化合物的成键和电子特性的性质。本文报道了这三种化合物的合成、晶体结构、拉曼光谱和发光行为。
The hydrothermal reaction of uranium trioxide and methylenediphosphonic acid in the presence of silver nitrate resulted in the formation of three new uranyl coordination polymers: AgUO2[CH2(PO3)(PO3H)] (Ag-1), [Ag2(H2O)1.5]{(UO2)2[CH2(PO3)2]F2}·(H2O)0.5 (Ag-2), and Ag2UO2[CH2(PO3)2] (Ag-3). All consist of uranyl pentagonal bipyramids that form two-dimensional layered structures. Ag-1 and Ag-3 possess the same structural building unit, but the structures are different; Ag-3 is formed through edge-sharing of F atoms to form UO5F2 dimers. The pH and silver cation have significant effects on the structure that is synthesized. Raman spectra of single crystals of Ag-1, Ag-2, and Ag-3 reveal v1 UO2(2+) symmetric stretches of 816 and 829, 822, and 802 cm(-1), respectively. Electronic structure calculations were performed using the projector augmented wave (PAW) method with density functional theory (DFT) to gain insight into the nature of bonding and electronic characteristics of the synthesized compounds. Herein, we report the syntheses, crystal structures, Raman spectroscopy, and luminescent behavior of these three compounds.