摘要
本论文以9种卤代苯甲酸为第一配体,以1,10-邻菲啰啉为中性第二配体，合成了18种铕、铽的三元配合物、6种含硝酸根配体的铕、铽四元配合物和8种稀土掺杂的铕、铽配合物。通过元素分析(C、N、H)和EDTA配位滴定,初步确定了这些配合物的组成。
用IR、TG-DTG、SEM等手段对铕的配合物进行了表征和性质研究。在这些配合物中,Eu(Ⅲ)和Tb(Ⅲ)与羧基氧原子和中性配体的氮原子形成了稳定的化学键。这些配合物均有较好的热稳定性。用X-射线单晶衍射测定了3个三元配合物Eu(p-FBA)3phen·H2O(1)、Tb(o-FBA)3phen (2)和Tb(p-FBA)3phen(3)的晶体结构。配合物均以双核分子形式存在,配合物1和3属三斜晶系,P1空间群,2属于单斜晶系,P2(1)/c空间群。晶胞参数分别为:(1) a = 8.3682(7) (?), b = 12.7584(11) (?), c = 14.9215(13) (?);α= 96.7310(10) (?),β=103.0540(10) (?),γ= 78.7890(10) (?); (2) a = 19.9178(13) (?), b = 15.1536(10) (?), c = 20.5664(14) (?);α= 90 (?),β=109.8590(10) (?),γ= 90 (?)。(3) a = 9.8875(10)(?), b = 11.7744(12) (?), c = 14.7646(16) (?);α= 111.9060(10) (?),β= 101.5230(10) (?),γ= 101.5830(10) (?)。
荧光光谱研究发现,这些配合物对应中心离子Eu(III)或者Tb(III)各个跃迁的荧光发射峰位置基本不变,但由于配体不同或引入不同掺杂离子,各配合物的发射强度明显不同。
本论文主要工作集中在:(1)研究了卤代苯甲酸上不同种类、不同位置的取代原子对Eu(III)、Tb(III)发光强度的影响。(2)比较得出各个系列配合物中发光强度最大的配合物。(3)培养单晶体,以期进一步研究晶体结构与配合物荧光性能之间的关系。(4)研究了引入硝酸根形成四元配合物后,硝酸根对Eu(III)、Tb(III)发光强度的影响。(5)研究了掺杂稀土离子对Eu(III)、Tb(III)发光强度的影响。所有这些研究,为进一步研制新的高效稀土发光材料提供了一定科学依据。
Eighteen ternary complexes of Eu(III) and Tb(Ⅲ), six quaternary complexes of Eu(III) and Tb(Ⅲ) mixed with NO3-, eight quaternary complexes of Eu(III) and Tb(Ⅲ) doped with Y(III) or Gd(III) have been synthesized. In these complexes, nine halogen-benzoic acids were used as the first ligand, and 1,10-phenanthroline as the second neutral ligand. The compositions of these complexes were confirmed by elemental analysis (C, H, N) and EDTA titration for rare earth.
The complexes were characterized by means of IR, UV, TG-DTG and SEM methods. In these complexes, the Eu(III) and Tb(Ⅲ)ions were bonded to the oxygen atoms of carboxylate and the nitrogen atoms of neutral ligands. These complexes show good thermal stability. The structures of three ternary complexes Eu(p-FBA)3phen·H2O (1), Tb(o-FBA)3phen (2) and Tb(p-FBA)3phen (3) have been determined using X-ray diffraction. They exist as binuclear molecules, 1 and 3 crystallize in triclinic, space group P1. 2 crystallize in monoclinic, space group P2(1)/c. The crystallographic parameters are as follows: (1) a = 8.3682(7) (?), b = 12.7584(11) (?), c = 14.9215(13) (?);α= 96.7310(10) (?),β=103.0540(10) (?),γ= 78.7890(10) (?); (2) a = 19.9178(13) (?), b = 15.1536(10) (?), c = 20.5664(14) (?);α= 90 (?),β=109.8590(10) (?),γ= 90 (?). (3) a = 9.8875(10) (?), b = 11.7744(12) (?), c = 14.7646(16) (?);α= 111.9060(10) (?),β= 101.5230(10) (?),γ= 101.5830(10) (?).
The luminescence spectra of the complexes show that the characteristic emission peaks of Eu(III) and Tb(III) remain unchanged. However, the emission intensity of the complexes changes due to the different ligands or different doped metal ions. The major works in this paper are focused on: (i) the influence of different substituents on the luminescent intensity; (ii) the best luminescent complex is figured out in each series; (ⅲ) cultivate single crystals to explain the relationship of the structure with the luminescence; (ⅳ) the influence of NO_3~- on the luminescent intensity; (v) the influence of the doped rare earth ions on the luminescent intensity. These results will provide valuable information for the synthesis of new effective rare earth luminescent materials.
引文
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