稀土芳香多羧酸配合物的合成及荧光性能研究

【作者】 杨芳；

【导师】 宋会花；

【作者基本信息】 河北师范大学 ， 无机化学， 2007， 硕士

【摘要】 自1972年前苏联研究人员报道了稀土芳香羧酸配合物的发光后,有关稀土芳香羧酸配合物的研究一直十分活跃。与有机化合物相比,稀土芳香羧酸配合物的荧光具有单色性好、发光强度高等特点,是一类有价值的发光材料。合成配合物的方法有常规溶液反应法、凝胶扩散法、水热法、溶剂热法、溶胶-凝胶法及流变相反应法等,其中水热法合成的晶体具有纯度高、缺陷少、热应力小、质量好等特点。被广泛的用来制备配位聚合物的晶体。本论文用水热法合成了以下几个系列的配合物并获得了两个配合物的单晶:（1）以1,3,5-均苯三甲酸为配体,铽为中心离子合成了两个系列的发光配合物:均苯三甲酸铽钆(Tb_xGd_1-xBTC·0.5H₂O),均苯三甲酸铽钇（TbxY（1-x）BTC·0.5H2O）（x=1, 0.9, 0.7, 0.5, 0.3, 0.1）。通过元素分析,EDTA配位滴定初步确定了配合物的组成。通过红外光谱,热重分析,荧光光谱等对配合物进行了初步的性质表征。通过对荧光光谱的研究发现,不发光的稀土离子Gd³⁺,Y³⁺的掺入,使配合物的荧光强度明显增强而发射峰的位置基本不变。本论文对掺杂离子对配合物的荧光强度的敏化作用进行了对比讨论,并确定了掺杂离子的最佳掺杂比例。（2）以1,3,5-均苯三甲酸为配体,铕为中心离子合成了两个系列的发光配合物:均苯三甲酸铕钆(Eu_xGd_1-xBTC·0.5H₂O),均苯三甲酸铕钇(Eu_xY_1-xBTC·0.5H₂O)（x=1, 0.9, 0.7, 0.5, 0.3, 0.1）。通过元素分析,EDTA配位滴定初步确定了配合物的组成。通过红外光谱,热重分析,荧光光谱等对配合物进行了初步的性质表征。通过对荧光光谱的研究发现,不发光的稀土离子Gd³⁺,Y³⁺的掺入,使配合物的荧光强度明显增强而发射峰的位置基本不变。本论文对掺杂离子对配合物的荧光强度的敏化作用进行了对比讨论,并确定了掺杂离子的最佳掺杂比例。（3）以3,4-吡啶二甲酸为配体,以铕、铽为中心离子合成了四个配位聚合物,Eu₂（C₇H₃NO₄）₃.4H₂O（1）、Eu₂（C₇H₃NO₄）₃(C₁₂H₈N₂)（H₂O）.H₂O（2）、Tb₂（C₇H₃NO₄）₃.4H₂O（3）、Tb₂（C₇H₃NO₄）₃(C₁₂H₈N₂)（H₂O）.H₂O（4）。并用X-射线单晶衍射仪测定了配合物（2）、（4）的晶体结构。晶体结构属于三斜晶系,P1空间群,其晶胞参数分别为: （2） a=7.5670 （ 15 ） , b=12.662（3）, c=18.384（4）;α=70.82（3）°,β=78.96（3）°,γ=76.02（3）°. （4） a=7.5288, b=12.6329（18）, c=18.320（3）;α=70.680（2）°β=79.074（2）°,γ=76.231（2）°。Eu, Tb有两种配位环境Eu1,Eu2;Tb1,Tb2。每个金属离子都是9配位形成三冠三棱柱的几何构型。Eu1（Tb1）与来自3,4-吡啶二羧酸中的7个O原子和配位水中的2个O原子配位,Eu2（Tb2）与来自3,4-吡啶二羧酸中的7个O原子和邻菲啰啉中的两个N原子配位,相邻的金属离子通过3,4-吡啶二羧酸桥联成一维带状链结构。此外,还对配合物（1）和（2）与（3）和（4）的荧光性质进行了对比讨论。更多还原

【Abstract】 Rare earth Aromatic carboxylate complex has been reported since 1972, As valueable luminescence material the rare earth aromatic carboxylate complex has the merits of good luminescence quality, high luminescence intensity et al. In recent years much attention has been focused on the study of rare earth aromatic carboxylate complexes. The methods of synthesizing the comples have solution reaction method、gel-diffusion method、hydrothermal synthesis method、sol-gel method et al. Among these methods the crystal synthesized by hydrothermal synthesis method has the merits of higy pure、low disfigurement、low heat stress、high quality et al. So the method has been widely used to prepare single crystal. In this paper serieses complexes were synthesized by hydrothermal synthesis method and two single crystal structure was determined by X-ray diffraction. The results as follows:（1） 1,3,5-benzenetricarboxylate（H₃BTC） was used as ligand. Tb、Y（Gd） as metal ions, two serieses complexes were synthesized in this paper, they are: Tb_xY_1-xBTC·0.5H₂O, Tb_xGd_1-xBTC·0.5H₂O, The properties of these complexes were charactered by means of IR, TG, and fluorescence spectrum. The fluorescence spectrum of these complexes show that the emission intensity of the complexes can be greatly enhanced when Tb³⁺ was substituted by doped Gd3+ or Y3+, while the position of the emission peaks remain unchanged. In this paper we analysis the sensitize role of the doped rare ions, decided the best doped proportion, and compared the fluorescence intensity with different doped rare earth ion.（2） 1,3,5-benzenetricarboxylate（H3BTC） was used as ligand. Eu、Y（Gd） as metal ions, two serieses complexes were synthesized in this paper, they are: Eu_xY_1-xBTC·0.5H₂O, Eu_xGd_1-xBTC·0.5H₂O, The properties of these complexes were charactered by means of IR, TG, and fluorescence spectrum. The fluorescence spectrum of these complexes show that the emission intensity of the complexes can be greatly enhanced when Eu3+ was substituted by doped Gd³⁺ or Y³⁺, while the position of the emission peaks remain unchanged. In this paper we analysis the sensitize role of the doped rare ions, decided the best doped proportion,. and compared the fluorescence intensity with different doped rare earth ion. （3） 3,4-pyridinedicarboxylate was used as ligands, Eu（Tb） as metal ions, four complexes were synthesis, they were: Eu2（C₇H₃NO₄）₃.4H₂O（1）、Eu2（C₇H₃NO₄）₃(C₁₂H₈N₂)（H₂O）.H₂O（2）、Tb2（C₇H₃NO₄）₃.4H₂O（3）、Tb2（C₇H₃NO₄）₃(C₁₂H₈N₂)（H₂O）.H₂O（4）. Complexes （2） （4）were determined by X-ray diffraction. their crystal structures are triclinic, space group P1 with （2） a=7.5670（15）, b=12.662（3）, c=18.384（4）;α=70.82（3）°,β=78.96（3）°,γ=76.02（3）°. （4） a=7.5288, b=12.6329（18）, c=18.320（3）;α=70.680（2）°β=79.074（2）°,γ=76.231（2）°. Eu（Tb） has two coordination environment Eu1,Eu2（Tb1,Tb2）. Each metal is nine-coordinated and formed tricapped trigonal prism geometry. Eu1（Tb1） was coordinated with nine O atom , seven coming from 3,4-pyridinedicarboxylate and two coming from coordinated water. Eu2（Tb2） was coordinated with seven O atom coming from 3,4-pyridinedicarboxylate and two N atom coming from phen. The bordered metal ions are linked into one dimensional broad band chains through bridhing 3,4-pyridinecarboxylate liagands. Besides, we discussed the difference of the fluorescence property of （1） and （2）; （3） and （4）.更多还原