Complexation of Uranyl Ion with Sulfonates: One- to Three-Dimensional Assemblies with 1,5- and 2,7-Naphthalenedisulfonates
Complexation of Uranyl Ion with Sulfonates: One- to Three-Dimensional Assemblies with 1,5- and 2,7-Naphthalenedisulfonates
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DOI：
10.1002/ejic.201601374
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发表时间：
2017-02
影响因子：
2.3
通讯作者：
P. Thuéry;J. Harrowfield
中科院分区：
文献类型：
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作者：
P. Thuéry;J. Harrowfield
硝酸铀酰与1，5-或2，7-萘二磺酸钠盐（分别为1，5-ndsNa_2和2，7-ndsNa_2）在（溶剂）水热条件下，在附加配体和/或金属阳离子存在下反应，得到6个新的配合物，并对其晶体结构进行了表征。[UO_2（1，5-nds）（H_2 O）]（1）晶体为三维（3D）骨架，两个磺酸基以O，O-桥连方式配位。在2，2 ′-联吡啶（bipy）或1，10-菲咯啉（phen）存在下，合成了三种配合物[（UO 2）2（1，5-nds）（OH）2（bipy）2]·H2O（2），[（UO 2）2（1，5-nds）（OH）2（bipy）2]·bipy（3）和[（UO 2）2（1，5-nds）（OH）2（phen）2]（4），其中双氢氧化物桥接的铀酰二聚体通过双（单齿）二磺酸盐配体组装成一维（1D）链。配合物[Cu（bipy）_2Cl][UO_2（2，7-nds）（OH）]·H_2O（5）呈现二维阴离子结构，其中单齿/O，O-桥连二磺酸配体连接氢氧桥连铀酰二聚体。在另外的葫芦[6]脲（CB 6）存在下，配合物[（UO 2）4 Na 4（2，7-nds）2（CB 6）Cl 4 O2（H2O）10]·5 H2O（6）结晶为具有复杂结构的三维骨架，双（β 3-氧代）桥联的铀酰四核部分通过双O，O β-桥联二磺酸根连接到CB 6结合的钠阳离子上。配合物2和4在固态下显示出强烈且分辨良好的铀酰发射，而在3和5中观察到几乎完全猝灭。
Uranyl nitrate was reacted with the sodium salt of either 1,5- or 2,7-naphthalenedisulfonate (1,5-ndsNa2 and 2,7-ndsNa2, respectively) under (solvo)-hydrothermal conditions, in the presence of additional coligands and/or metal cations, to give six new complexes which were characterized by their crystal structure determinations. [UO2(1,5-nds)(H2O)] (1) crystallizes as a three-dimensional (3D) framework, with both sulfonate groups coordinated in the O,Oʹ-bridging mode. In the presence of the N-chelating species 2,2ʹ-bipyridine (bipy) or 1,10-phenanthroline (phen), the three complexes [(UO2)2(1,5-nds)(OH)2(bipy)2]H2O (2), [(UO2)2(1,5-nds)(OH)2(bipy)2]bipy (3) and [(UO2)2(1,5-nds)(OH)2(phen)2] (4) were obtained, in which doubly hydroxide-bridged uranyl dimers are assembled into one-dimensional (1D) chains by bis(unidentate) disulfonate ligands. The complex [Cu(bipy)2Cl][UO2(2,7-nds)(OH)]H2O (5) displays anionic, two-dimensional (2D) sheets in which unidentate/O,Oʹ-bridging disulfonate ligands link hydroxide-bridged uranyl dimers. In the additional presence of cucurbit[6]uril (CB6), the complex [(UO2)4Na4(2,7-nds)2(CB6)Cl4O2(H2O)10]5H2O (6) crystallizes as a 3D framework of intricate architecture, with bis(3-oxo) bridged uranyl tetranuclear moieties connected to CB6-bound sodium cations by doubly O,Oʹ-bridging disulfonates. Complexes 2 and 4 display intense and well-resolved uranyl emission in the solid state, while nearly complete quenching is observed in 3 and 5.