两个多酸基镧系(Eu、Tb)双膦酸酯配合物的合成、物化性质和太赫兹时域光谱

Synthesis,physicochemical properties and terahertz time domain spectroscopy of two lanthanide(Eu,Tb) bisphosphonate complexes containing keggin polyoxometalates

在乙腈和去离子水的混合溶剂中合成了2个新的多酸基镧系双膦酸酯配合物[Eu(L)_(4)]PW_(12)O_(40)·2CH_(3)CN (1)和[Tb(L)_(3)(H_(2)O)]PW_(12)O_(40)(2)(L=亚乙基二膦酸四乙酯),并通过单晶X射线衍射、元素分析、红外光谱、粉末X射线衍射、热重分析和太赫兹时域光谱对2个配合物的性质进行了表征,分析了配合物的晶体结构及分子间弱作用力,研究了配合物的发光等性能。单晶结构表明,配合物1是以Eu(Ⅲ)为中心、L为配体螯合形成的扭曲四方反棱柱结构。配合物2是以Tb(Ⅲ)为中心、L和H_(2)O为配体形成的扭曲单帽八面体结构。发光光谱表明配合物1和2所有的发射峰来源于金属内部的电荷迁移。此外,太赫兹时域光谱对配合物1和2的结构和发光的分析提供了帮助。

Two novel lanthanide bisphosphonate complexes containing Keggin polyoxometalates [Eu(L)_(4)]PW_(12)O_(40)·2CH_(3)CN(1) and [Tb(L)_(3)(H_(2)O)]PW_(12)O_(40)(2)(L=tetraethyl ethylenediphosphonate) were synthesized in a mixed solvent of acetonitrile and deionized water.The properties of the two complexes were characterized by single-crystal X-ray diffraction,elemental analysis,infrared spectroscopy,powder X-ray diffraction,thermogravimetric analysis and terahertz time domain spectroscopy.The crystal structure and intermolecular weak force of the complexes were analyzed,and the luminescence and other properties of the complexes were studied.The single crystal X-ray diffraction indicates that the structure of complex 1 is a twisted tetragonal antiprism with Eu(Ⅲ) as the center and L as the ligands chelate.The structure of complex 2 is a twisted single-capped octahedral with Tb(Ⅲ) as the center and L and H_(2)O as the ligands.The luminescence spectra indicate that all emission peaks of complexes 1 and 2 are due to charge transfer within the metal.In addition,terahertz time-domain spectroscopy has helped in the study of complexes 1 and 2.CCDC:2321285,1;,2321286,2.