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Synthesis and physical property of uranium-containing porous coordination polymer

含铀多孔配位聚合物的合成及物性

基本信息

批准号：
22760679
负责人：
AOYAGI Noboru
金额：
$ 2.75万
依托单位：
Japan Atomic Energy Agency
依托单位国家：
日本
项目类别：
Grant-in-Aid for Young Scientists (B)
财政年份：
2010
资助国家：
日本
起止时间：
2010 至 2011
项目状态：
已结题

项目摘要

The colors of the multi-valent complexes of uranium, neptunium and plutonium strongly depend on the oxidation state of the metal ion, and it is often possible to determine the oxidation state of the metal ion from the color of its solutions. Given the fact that uranium is only weakly radioactive due to the long half-lives of its naturally occurring isotopes, uranium-containing compounds could find some applications as advanced materials.In the present study, temperature-dependent yellow-to-red colour changes of uranyl thiocyanate complexes with 1-alkyl-3-methylimidazolium cations have been studied by different spectroscopic methods and this phenomenon is attributed to changes in the local environment of the uranyl ion, including the coordination number, as well as to cation. anion interactions.The structure contained disorder in three of the NCS^-anions and one C_2mim^+cation. The U-O bond distances(1.766(8), 1.765(9) A) and the O-U-O bond angle(171.2(9) 1°) are in the range expected for the uranyl moiety. The mean U-N distance is 2.45 A which is close to that seen in[DPSH]_3[UO_2(SCN)_5](DPSH=2-pyridylthio-2-pyridinium) and Cs_3[UO_2(SCN)_5] which both have mean U-N distances of 2.45 A. However, in this structure there are large variations from the mean with much shorter distances(U-N=2.398(11) A) and large distances(U-N=2.513(10) A), Time-resolved luminescence spectra, at 77 K, of neat uranyl which have not been known for uranyl-thiocyanates. The anisotropic structure could play an important role in the chromic reactions. Due to the weak interaction between the thiocyanate and imidazolium cation, labile and flexible coordination geometries for thiocyanate are allowed.

铀、镎和钚的多价络合物的颜色很大程度上取决于金属离子的氧化态，并且通常可以从其溶液的颜色确定金属离子的氧化态。由于铀的天然同位素半衰期很长，因此铀只有微弱的放射性，因此含铀化合物可以作为先进材料得到一些应用。硫氰酸铀酰与1-烷基-3-甲基咪唑阳离子已经通过不同的光谱方法进行了研究，这种现象是由于局部环境的变化，铀酰离子，包括配位数，以及阳离子。该结构包含三个NCS^-阴离子和一个C_2mim^+阳离子的无序结构。U-O键距（1.766（8），1.765（9）A）和O-U-O键角（171.2（9）1°）在铀酰部分预期的范围内。[DPSH]_3[UO_2（SCN）_5]（DPSH=2-吡啶硫基-2-吡啶）和Cs_3[UO_2（SCN）_5]的U-N平均距离均为2.45。然而，在这种结构中，有很大的变化，从平均值与短得多的距离（U-N=2.398（11）A）和大的距离（U-N=2.513（10）A），时间分辨发光光谱，在77 K，纯铀酰还没有已知的铀酰硫氰酸盐。这种各向异性结构在显色反应中可能起重要作用。由于硫氰酸盐和咪唑阳离子之间的弱相互作用，允许硫氰酸盐的不稳定和灵活的配位几何形状。