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锕系元素的富氮化合物:六氧化二铀(VI) 5,5'-偶氮双[四唑啉]五水合物及其异常小的铀酰角。

Nitrogen-rich compounds of the actinoids: dioxouranium(VI) 5,5'-azobis[tetrazolide] pentahydrate and its unusually small uranyl angle.

机构信息

Vienna University of Technology, Atominstitut, Stadionallee 2, 1020 Vienna, Austria.

出版信息

Inorg Chem. 2012 Jun 18;51(12):6739-45. doi: 10.1021/ic300377j. Epub 2012 May 31.

Abstract

Uranyl(VI) 5,5'-azobis[tetrazolide] pentahydrate was synthesized and characterized using X-ray crystallography, elemental analysis, UV/vis, MIR, FIR, and Raman spectroscopy. It is the second-most nitrogen rich compound of uranium (26.72 wt % N) and only the second structurally characterized uranium complex with a tetrazole ligand described in the literature. The compound's structure is characterized by an exceptionally small uranyl angle of 172.4(1)°, which provides information on the coordination properties of tetrazole ligands as they affect the donor's environment by strong steric and perhaps electrostatic repulsion. The compound showed luminescence under excitation with a near UV laser. The mean lifetime of its excited state was shorter than in the case of UO(2)(NO(3))(2)·6H(2)O, indicating quenching by the ligand. Despite its high nitrogen content (and thus potentially explosive character), the title compound proved to be stable even under neutron radiation causing induced fission processes.

摘要

铀酰(VI)5,5'-偶氮[四唑]五水合物是通过 X 射线晶体学、元素分析、紫外/可见、MIR、FIR 和拉曼光谱进行合成和表征的。它是铀的第二富氮化合物(26.72wt%N),也是文献中描述的第二个具有四唑配体的结构特征的铀配合物。该化合物的结构特征是铀酰角非常小,为 172.4(1)°,这提供了有关四唑配体的配位性质的信息,因为它们通过强烈的空间和可能的静电排斥作用影响供体的环境。该化合物在近紫外激光激发下显示出发光。其激发态的平均寿命短于 UO(2)(NO(3))(2)·6H(2)O,表明配体的猝灭作用。尽管该标题化合物的含氮量很高(因此可能具有爆炸性),但即使在中子辐射引起的裂变过程下,它也被证明是稳定的。

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