【作者】 刘静；

【导师】 夏光明；

【作者基本信息】 济南大学 ， 应用化学， 2012， 硕士

【摘要】 稀土离子配合物发光材料具有光纯度高、受环境影响小等优点，在光波导、OLEDs（有机电致发光器件）、荧光探针等领域具有广泛的应用前景。稀土离子自身吸收能力弱，将镧系离子与配体配位后通过天线效应提高了镧系离子的发光强度，且保持其特征发射光谱。但配合物材料中存在配体与中心离子间能量传递效率低、配体与中心离子竞争性发光等因素导致材料发光性能降低，影响材料的应用。当前研究关于手性配体对材料结构及发光性能的影响也较少。根据文献综述，我们发现对于手性配体与稀土离子形成的稀土配合物已有报道，但是关于手性噻吩衍生物的稀土配合物的研究很少，而噻吩环中的硫原子可以促进能量由单重激发态S1到最低三重激发态T1的转移，我们拟以L-或者D-氨基酸与噻吩环形成的衍生物作为配体研究手性配合物的性质。本论文合成了以噻吩为母核的手性酰胺类化合物作为第一配体，Ni（NO₃）_2·6H₂O、ZnO、Cu（NO₃）_2·3H₂O、CuO作为第二种金属离子，邻菲啰啉、4,4’-联吡啶作为第二配体，与镧系离子（Ln=Eu、Sm、Dy、Tb）合成了4种掺杂的铕配合物和7种稀土三元配合物，得到了6种稀土配合物和三种手性配体的单晶。通过IR、单晶衍射等对配体和配合物进行了表征和性质研究。本论文工作主要分为以下几部分：1、以2,5-噻吩二甲酸与氯化亚砜得到的酰氯为起始反应物，分别与L-亮氨酸甲酯盐酸盐、L-缬氨酸甲酯盐酸盐、L-异亮氨酸甲酯盐酸盐、L-丙氨酸甲酯盐酸盐、D-丙氨酸甲酯盐酸盐反应得到五种手性配体，通过解酯反应得到五种对应的羧酸，同时得到了2,5-噻吩二甲酰基-L-异亮氨酸、2,5-噻吩二甲酰基-L-缬氨酸甲酯、2,5-噻吩二甲酰基-D-丙氨酸甲酯的单晶。2、以2,5-噻吩二甲酰基-L-亮氨酸为第一配体，铕离子为第一金属离子，分别与Ni（NO₃）_2·6H₂O、ZnO、Cu（NO₃）_2·3H₂O、CuO、邻菲啰啉（第二配体）在水热条件下反应得到五种铕配合物，通过红外、荧光进行了相关谱学表征。Zn（Ⅱ）提高了Eu（Ⅲ）离子的发光强度，而Ni（Ⅱ）和Cu（Ⅱ）对Eu（Ⅲ）离子的发光具有淬灭作用。3、以2,5-噻吩二甲酰基-L-丙氨酸和2,5-噻吩二甲酰基-D-丙氨酸为第一配体，4,4’-联吡啶为第二配体，用水热法合成了四种铕和钐配合物，通过IR、TG-DTA、单晶衍射对其进行了表征，确定了配合物的结构。通过比较，发现两种手性配体形成的配合物的单晶结构是相似的，是双核结构，不同的是游离水的位置，IR、TG-DTA和光致发光的性质也是相似的。4、以2,5-噻吩二甲酰基-L-丙氨酸为第一配体，4,4’-联吡啶为第二配体，用水热法合成了两种镝和铽配合物，通过IR、TG-DTA、荧光和单晶衍射对其进行了表征，配合物分别表现了镝和铽的特征荧光。Tb（Ⅲ）离子存在特征发射，特别的是5^D₄→7^F₃跃迁的强度仅次于5^D₄→7^F₅跃迁的强度，这是很少见的。更多还原

【Abstract】 Lanthanide coordination polymers have the advantages of high purity and weakinfluences of environment, which has a broad prospect of application in optical waveguide,OLEDs （organic light-emitting diodes） and fluorescent probe fields. Absorption ability of rareearth ions is weak, ligand that coordinated with lanthanide ion improves luminescent intensitythrough antenna effect, which makes lanthanide ion retaining the emission spectrumcharacteristics. But lanthanide coordination polymers have some factors to reduceluminescent and affect the application of materials. These factors contain low energy transferefficiency and competitive luminescence between ligand with center ions. The currentresearch about influence on material structure and luminescent properties of chiral ligands isless.According to the literature review, we found that the rare earth complexes formed bycoordination of chiral ligands and rare earth ions have been reported, yet researches on rareearth complexes of chiral thiophene derivatives were rarely explored. Considerring the S atomin thiophene ring can contribute to the energy transfer from single excited state S1to thelowest triplet excited state T1, we plan to synthetise complexes using L/D-amino acid andthiophene derivatives as ligand, and study the nature of chiral complexes. Four dopedeuropium complexes and seven rare earth complexes （Ln=Eu, Sm, Dy, Tb） have beensynthesized. In these complexes, thiophene-amide compound as the first ligand andNi（NO₃）_2·6H₂O, ZnO, Cu（NO₃）_2·3H₂O and CuO as the second metal ion and1,10-phen,4,4’-bipyridine as the second ligand. In addition, we obtained the crystal structures of six rareearth complexes and three chiral ligands. The properties of ligands and complexes arecharacterized by IR、X-ray diffraction.The thesis consists of the following several parts:1、The thiophene-2,5-dicarbonylic dichloride is regarded as a core of ligand, which hasobtained with thiophene-2,5-dicarboxylic acid and sulfoxide chloride. Five chiral ligandswere obtained via the reactions of L-leucine methyl ester hydrochloride、L-valine methyl esterhydrochloride、 L-isoleucine methyl ester hydrochloride、 L-alanine methyl esterhydrochloride、D-alanine methyl ester hydrochloride. Then on the base of amides, five kinds of carboxylic acid were obtained by the hydrolyzation of ester. Furthermore, the crystalstructures of2,5-thiophenedicarboxyl-L-isoleucine acid、2,5-thiophenedicarboxyl-L-valineacid and2,5-thiophenedicarboxyl-D-alanine acid.2、Five europium complexes were obtained in hydrothermal conditions. In thesecomplexes,2,5-thiophenedicarboxyl-L-leucine acid as the first ligand, which reactrespectively with Ni（NO₃）_2·6H₂O, ZnO, Cu（NO₃）_2·3H₂O, CuO and1,10-phen（the secondligand）. The properties of complexes are characterized by IR and fluorescence. Zn（Ⅱ） metalion increased luminescent intensity of Eu（Ⅲ） ion, while Ni（Ⅱ） and Cu（Ⅱ）ions have aquenching effect on luminescence of Eu（Ⅲ） ion.3、Four europium and samarium complexes were obtained in hydrothermal conditions. Inthese complexes,2,5-thiophenedicarboxyl-L-alanine acid and2,5-thiophenedicarboxyl-D-alanine acid as the first ligand,4,4’-bipyridine as the second ligand. The properties ofcomplexes are characterized by IR、TG-DTA and X-ray diffraction. we obtained the crystalstructures of four rare earth complexes. The crystal structures are similar with two chiralcomplexes. The coordination environment of rare earth ions and position of free water aredifferent. The properties of IR、TG-DTA and photo-induced luminescence are similar.4、Two dysprosium and terbium complexes were obtained in hydrothermal conditions. Inthese complexes,2,5-thiophenedicarboxyl-L-alanine acid as the first ligand,4,4’-bipyridine asthe second ligand. The properties of complexes are characterized by IR、TG-DTA、fluorescence and X-ray diffraction. The complexes emit characteristic light of Dy³⁺ion andTb³⁺ion. The luminescence of Tb³⁺ion is particular, the intensity of5^D₄→7^F₃transition isbetter for the intensity of5^D₄→7^F₅transition.更多还原