一例U-Ag杂金属半刚性羧酸配体配合物的制备及性质研究

Synthesis and Properties of U-Ag Heterometallic Complex from Semi-rigid Carboxylic Ligand

为了深入研究锕系元素的配位行为,基于半刚性羧酸配体3-(羧基甲氧基)苯甲酸(H_(2)L),合成了一个三维结构的U-Ag杂金属配合物[(L)(HL)Ag(UO_(2))](简称UAgL)。通过X-射线单晶衍射、红外光谱、紫外光谱及X-射线粉末衍射对其晶体结构进行了表征,结果显示,配合物UAgL中铀原子处于稍变形的五角双锥配位环境中,银原子则处于五配位的四方锥配位环境中。铀酰离子中的氧原子参与配位且处于轴向位置,完全脱质子的配体L和部分脱质子的配体HL则采取两种配位模式将铀中心与银中心连接成二维层状结构,层状结构之间又通过铀酰氧原子连接成三维的网络结构。进一步探讨了配合物UAgL的热稳定性和在室温下的固态荧光性质,认为其可作为潜在的光致发光材料。

In order to further study the coordination behavior of actinides,a three-dimensional U-Ag heterometallic complex[(L)(HL)Ag(UO_(2))](UAgL)was synthesized by the semi-rigid carboxylic acid ligand H_(2)L,where H_(2)L is 3-(carboxymethoxy)benzoic acid.The crystal structure of complex UAgL was characterized by X-ray single crystal diffraction,IR spectrum,UV spectrum and X-ray powder diffraction.The uranium atom in complex UAgL is in a slightly distorted pentagonal bipyramidal coordination environment,while the silver atom is in a pentagonal bipyramidal coordination environment.The oxygen atom from the UO_(2)^(2+)also coordinates to silver atom and it is located in the axial position.The fully deprotonated ligand L and partially deprotonated ligand HL adopt two coordination modes to connect the uranium center and silver center into a two-dimensional layered structure,which is then connected by uranyl oxygen atoms to form a three-dimensional network structure.The thermal stability of the complex UAgL and its solid-state fluorescence properties was further investigated at room temperature.UAgL can be used as a future photoluminescent material.