【作者】 张兰芬；

【导师】 杨良准；

【作者基本信息】 上海师范大学 ， 应用化学， 2008， 硕士

【摘要】 本文合成了稀土元素Eu、Tb与有机配体1,10-邻菲罗啉,苯二甲酸的一系列稀土发光配合物。通过元素分析、红外谱图分析、荧光性能和差热-热重分析得到了稀土配合物的组成和结构信息,并得出以下结论:⑴研究了三组分不同滴加次序对稀土配合物的荧光强度的影响。通过实验,得到稀土配合物的最佳合成工艺,并得出结论:稀土元素先与配体1,10-邻菲罗啉中的N发生配位,再与苯二甲酸的羧酸氧发生配位。⑵比较苯二甲酸的两个羧酸根的不同取代位置对稀土三元配合物的荧光强度的影响,发现以对苯二甲酸为配体的三元配合物的荧光强度最大。对苯二甲酸的对称结构,有利于分子内能量的传递,并且和配体1,10-邻菲罗啉有较好的协同效应。⑶稀土Eu³⁺、Tb³⁺的三元配合物分别具有很强的红色、绿色荧光。当有机配体相同时,Tb³⁺的三元配合物荧光强度比Eu³⁺的荧光强度大。从有机配体与稀土元素Eu³⁺、Tb³⁺的能级分析可知,苯二甲酸的最低三重态能级和Tb³⁺的5D4能级匹配要比与Eu³⁺的5D0能级匹配的效果要好,所以在具有相同有机配体情况下,Tb³⁺的三元配合物的荧光强度比相应Eu³⁺的三元配合物的荧光强度强。另外本文还将具有荧光性能高、单色性能强的稀土配合物Eu（Phen）2Cl3掺杂到具有高比表面积和大孔径的分子筛MCM-41和MCM-48中,得到了一系列具有高荧光性能和强热稳定性的有机-无机杂化材料。XRD、N₂吸附-脱附、红外、荧光等测试手段均表明配合物掺入到分子筛的孔道中。该法制备的杂化材料在发光材料领域有一定的应用前景,同时该材料具有以下特性:⑴采用最佳合成方法制备出具有高比表面积和大孔径的分子筛MCM-41和MCM-48,在超声辅助的作用下,稀土配合物Eu（Phen）₂Cl₃在分子筛MCM-41和MCM-48中的最大掺杂量分别达到7.17 %和8.60 %。⑵杂化材料Eu（Phen）₂Cl₃/MCM-41（48）具有很强的荧光性能,Eu（Phen）₂Cl₃/MCM-41（7.17 %）的荧光强度是纯稀土配合物的42.6%,Eu（Phen）₂Cl₃/ MCM-48（8.60 %）的荧光强度是纯稀土配合物的50 %,分子筛的硅壁和稀土配合物之间的相互作用,使得杂化材料的荧光强度增大。⑶嵌入到分子筛孔道里的稀土配合物的热稳定性都较大程度的提高,Eu（Phen）₂Cl₃在MCM-41中分解温度提高了100 oC,在MCM-48中提高了近200 oC,这是由于稀土配合物嵌入到分子筛的孔道里面,孔道的特殊结构对稀土配合物有很好的保护作用,并且MCM-48的三维孔道比MCM-41的一维孔道结构效果更好,使得杂化材料Eu（Phen）₂Cl₃/MCM-48的热稳定性更高。更多还原

【Abstract】 In our study, a series of ternary complexes of rare earth (Eu³⁺、Tb³⁺) with Phthalic acids and 1,10-Phenanthroline were synthesized. The composition and structure of the resulting ternary lanthanide complex was established based on the elemental analysis results and further confirmed by IR spectra and DTA-TG., respectively. The photoluminesent of the products were examined by the PL spectum. Then we could get the conclusions as following:⑴We study the effection of the doping sequence of the three different components to the fluorescence of the complexes. Through the experiments, we got the fitting synthesis methods, and we could conclude that the rare-earth (Eu³⁺、Tb³⁺) coordinate with the nitrogen atom of 1,10-Phenanthroline （Phen） firstly, then coordinate with carboxyl-oxygen of Phthalic acids.⑵Analysis the fluorescence intensity of different replace dicarboxylic on benzene, it was shown that the ternary complexes with p-phthalate acid had the maximal fluorescence intensity. That due to the symmetry of p-phthalate acid which was advantaged for the energy transfer in the complex molecule, and it could cooperate with 1,10-Phenanthroline commendably, this function was good for the rare-earth ion.⑶The ternary complexes of Eu³⁺ with Phthalic acids and Phen emitted red-light, while the homologous of Tb³⁺ emitted green-light. When the ternary complexes with the same organic ligants, the ternary complexes of Tb³⁺ exhibited higher relative emission intensity, the causation is the matching effection between the ternary energy of Phthalic acids and 5D4 of Tb³⁺ advantaged than that of Eu³⁺. In this article we also synthesized MCM-41 and MCM-48 molecular sieve, which had high surface area and big pore volume and fitting pore diameter. A series of high luminescent and thermal stability dopant concentrations hybrid materials of Eu（Phen）₂Cl₃/MCM-41（48） have been synthesized by ultrasound technology. The characterization of XRD、N2-adsorption-desorption、FTIR and luminescence spectrum showed that the rare earth compound had doped into the holes of mesoporous material MCM-41 and MCM-48. At the same time, we also discussed the properities of the hybrid materials through a series of characterization and analyzed their potential uses in the filed of solid luminescent laser materials, biosensor, photoelectricity switch, flat display, etc. The as-prepared products had such charactorities as follows:⑴We synthesized the MCM-41 and MCM-48 using the proper methods, which had high surface area and big pore volume, then we steeped it into different concentrations of Eu（Phen）₂Cl₃ methyl alcohol solution, under the help of ultrasonic. The doping masses of Eu（Phen）₂Cl₃ were measured by ICP. The doping mass of the hybrid materials are improving with the increase of the concentrations of Eu（Phen）₂Cl₃ methyl alcohol solution. The maximal doping intensity of hybrid material Eu（Phen）₂Cl₃/MCM-41（48） are 7.17 % and 8.6 % respectively.⑵The luminescence intensities of Eu（Phen）₂Cl₃/MCM-41（48） increased with the increasing of the doping mass of Eu（Phen）₂Cl₃. The luminescence intensity of hybrid materials Eu（Phen）₂Cl₃/MCM-41（7.17%）and Eu（Phen）₂Cl₃/MCM-48（8.6 %） are 42.6 % and 50 % as high as the pure rare-earth compound, respectively. The luminescence intensities of hybrid materials are much improved, because of the interaction between the silica-bases composites and the rare-earth compound.⑶Compared to the pure rare-earth compound, the thermal stability of the hybrid materials Eu（Phen）₂Cl₃/MCM-41（48） enhances by about 100 oC and 200 oC, respectively. The hole-path of the molecular sieve protected the rare-earth compound from decompounding when it was heated, and the structure of MCM-48 molecular sieve was three-dimensional which was more available for the protection of Eu（Phen）₂Cl₃ than one-dimensional straight hole of MCM-41, so the hybrid materials of Eu（Phen）₂Cl₃/MCM-48 had very high thermal stability.更多还原