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双酰胺配体铕和铽混合固态配合物的光谱研究

期刊名称：光谱学与光谱分析,
时间：0
页码：1856-1861
语言：中文
分类：O614.3[理学—无机化学;理学—化学]
作者机构：[1]中国科学院兰州化学物理研究所,固体润滑国家重点实验室,甘肃兰州730000, [2]中国科学院研究生院,北京100864
相关基金：国家创新研究群体基金项目（50421502）和国家自然科学基金项目（50575217）资助
相关项目：空间润滑材料与技术研究

关键词：铕铽混合配合物, 共沉淀, 研磨, 荧光光谱, Eu and Tb mixed complexes, Coprecipitation, Grind, Fluorescent properties

中文摘要：

在氯仿和乙酸乙酯溶液中合成了以1,6-二[（2’-苄胺甲酰基）苯甲氧基]己烷（L）为配体的硝酸铕和硝酸铽配合物,以及不同摩尔比的铕和铽的共沉淀配合物,又按不同的摩尔比将单一的硝酸铕和硝酸铽配合物通过研磨混合,得到混合固态的铕铽配合物。通过元素分析、红外光谱、紫外光谱、XPS光电子能谱对配合物进行了表征,结果表明：单一稀土硝酸盐与配体形成的是2∶3型的配合物;所有的配合物都具有相似的配位结构;与单一稀土配合物相比,相同摩尔比的混合配合物的紫外吸收有所降低;混合配合物中发生了一定的化学键合作用,电子结合能有变化。通过荧光光谱对这些配合物的荧光性质进行了详细的研究,表明与单一的铕和铽配合物相比,两种混合固态配合物无论是荧光发射峰位还是荧光强度均发生了明显变化,铽对铕的荧光强度有很强的敏化作用,铕对铽的荧光强度有猝灭作用。在紫外灯的照射下,共沉淀配合物的荧光颜色随着摩尔比的变化呈现有规律的变化。

英文摘要：

Abstract In the present work, Eu （NO3）3 and Tb（NO3）3 complexes with a diamide ligand 1,6-bis[ （2 ＇-benzylaminoformyl） phenoxyl]hexane （L） were prepared in the solution of chloroform and ethyl acetate. Their mixed complexes with different molar ratio also synthesized by eopreeipitation. Eu and Tb complexes were mixed with different molar ratio, mechanically ground, and a series of mixed solid complexes were obtained. These mixed complexes were characterized by elemental analysis, UV-Vis, IR and XPS spectra. The analytical data were obtained by a Vario EL CHN and indicated that Eu and Tb complexes formed a 2 ： 3 metal-to-ligand stoiehiometries 2RE（NO3）3 · 3L · 4H2O. Their IR spectra were recorded on a Bruke FTS66V/S spectrophotometer. The results indicate that all complexes have similar IR spectra, of which the characteristic bands have similar shifts, suggesting that they have a similar coordination structure. UV-Vis spectra were recorded on a Hitachi U-3010 spectrophotometer and showed that under the influence of the mixed ions, the absorbanee of the mixed complexes is not identical with that of the pure complexes. XPS spectra were analyzed on a PHI-5702 X-ray photoelectron spectroscope （XPS） operating with monochromatic Mg Ka irradiation at pass energy of 29.4 eV. The binding energies of O（ls）, Eu（3d） and Tb（4d） in the two kinds of mixed complexes were changed compared with Eu-L and Tb-L complexes. This indicates that these two synthetic methods were not a simple physical mixing process, but there was some chemical effect between the mixed Eu-L and Tb-L complexes. The fluorescence spectra of the mixed complexes were obtained on a Hitachi F-4500 speetrophotometer at room temperature. The excitation and emission slit widths was 1.0 nm. It was concluded from the excitation spectra that the best excitation wavelengths for Eu and Tb complexes are 396 and 320 nm respectively. For the convenience of comparing the fluorescence intensities with each other, the excitation waveleng