酰胺型开链配体及其稀土配合物的合成、表征及荧光性质的研究
摘要
稀土元素具有优良的光学、电学和磁学性质，它能够通过与N，O等原子的配位与许多有机化合物形成配合物。在以镧系稀土离子为中心的稀土有机配合物中，有机配体能有效地通过天线效应将能量传递给中心离子，而稀土离子发光具有优异的单色性、发光强度高的特点，使得稀土配合物成为发光领域中的重要组成部分，如何设计配体结构以得到更好的荧光性能成为目前研究中的热点。酰胺型开链配体由于其具有结构可调和配位末端基可换等优点，一方面对稀土离子具有较好的识别配位作用，可以得到具有新奇结构的配合物，另一方面便于调整配体的末端功能基团以实现配位后更好的荧光性质，因此受到了广泛的关注。本论文报道了四个酰胺型开链配体及三个系列稀土配合物的合成，通过元素分析、红外、核磁、摩尔电导等手段对其结构进行了表征，并对稀土配合物的荧光性质进行了研究。全文包括五个部分：
1．概述了稀土配合物发光材料的研究现状及应用前景。
2．配体N，N'-(1，3-亚苯基)二皮考林酰胺(图1)及其稀土配合物的合成、表征和荧光性质的研究。研究表明，配体与稀土离子配合物的可能组成为：[REL(NO_3)_2]NO_3·H_2O(RE=La~(3+)、Eu~(3+)、Gd~(3+)、Tb~(3+))，其中Eu~(3+)和Tb~(3+)配合物具有良好的荧光性质，尤其是Eu~(3+)配合物荧光较强。
3．配体6-乙酰氨基-N，N-二乙基皮考林酰胺(图2)及其稀土配合物的合成、表征和荧光性质的研究。研究表明，配体与稀土离子配合物的可能组成为：[REL_2(NO_3)_2]NO_3·H_2O(RE=La~(3+)、Eu~(3+)、Tb~(3+))，其中Eu~(3+)、Tb~(3+)配合物具有良好的荧光性质，Tb~(3+)配合物的荧光较强。
4．配体6-乙酰氨基皮考林酸(图3)及其稀土配合物的合成、表征和荧光性质的研究。研究表明，配体与稀土离子配合物的可能组成为：REL_3·4H_2O(RE=La~(3+)、Eu~(3+)、Gd~(3+)、Tb~(3+))，其中Eu~(3+)、Tb~(3+)配合物具有良好的荧光性质，尤其是Eu~(3+)的荧光较强。
5．配体N~2，N~6-二(苯基氨基甲酰)吡啶-2，6-二甲酰胺(图4)的合成、表征。在合成稀土配合物时由于反应条件控制和配位方式复杂的原因未得到纯的配合物，有待于进一步的研究。
It is well known that rare earth complexes have excellent optical, electrical and magnetic properties. In these complexes, the energy can be transmitted effectively from the organic ligands to the center lanthanide ions through the antenna effect. So, the design of the ligands' structure to obtain more effective transmission becomes the key in the field of luminescene. Recently lanthanide complexes with open-chain amide ligands have attracted much attention mainly because the ligands have the unusual molecular structures: flexible chain, changeable terminal group and high selectivity and coordination to lanthanide ions.
In this dissertation, three series of open-chain amide ligands and their lanthanide complexes have been synthesized and characterized in details with elemental analyses, molar conductance, spectra (infrared, ~1HNMR, MS). The luminescence properties of the complexes have been investigated. The dissertation includes five aspects:
1. A brief view of the research progress in a variety of luminescent materials of lanthanide complexes and the prospect of rare earth complexes' application in many fields.
2. Synthesis and characterization of the ligand N,N'-(1,3-phenylene)dipicolinamide (Fig 1) and its rare earth complexes. The results indicated that the composition of the complexes is [REL(NO_3)_2]NO_3·H_2O (RE = La~(3+)、Eu~(3+)、Gd~(3+)、Tb~(3+)、). In these complexes, the europium complex exhibited characteristic fluorescence of europiumion.
3. Synthesis and characterization of the ligand6-acetamido-N,N-diethylpicolinamide (Fig 2) and its rare earth complexes. The results indicated that the composition of the complexes is [REL_2(NO_3)_2] NO_3·H_2O (RE = La~(3+),Eu~(3+)、Tb~(3+)). In these complexes, the terbium complex exhibited characteristic fluorescence of terbium ion.
4. Synthesis and characterization of the ligand 6-acetamidopicolinic acid (Fig 3) and its rare earth complexes. The results indicated that the composition of the complexes is REL_3·4H_2O (RE = La~(3+)、Eu~(3+)、Gd~(3+)、Tb~(3+)). In these complexes, the europium complex exhibited characteristic fluorescence of europium ion.
5. Synthesis and characterization of the ligand N~2,N~6-bis(phenylcarbamoyl)pyridine-2,6-dicarboxamide(Fig 4).
1．概述了稀土配合物发光材料的研究现状及应用前景。
2．配体N，N'-(1，3-亚苯基)二皮考林酰胺(图1)及其稀土配合物的合成、表征和荧光性质的研究。研究表明，配体与稀土离子配合物的可能组成为：[REL(NO_3)_2]NO_3·H_2O(RE=La~(3+)、Eu~(3+)、Gd~(3+)、Tb~(3+))，其中Eu~(3+)和Tb~(3+)配合物具有良好的荧光性质，尤其是Eu~(3+)配合物荧光较强。
3．配体6-乙酰氨基-N，N-二乙基皮考林酰胺(图2)及其稀土配合物的合成、表征和荧光性质的研究。研究表明，配体与稀土离子配合物的可能组成为：[REL_2(NO_3)_2]NO_3·H_2O(RE=La~(3+)、Eu~(3+)、Tb~(3+))，其中Eu~(3+)、Tb~(3+)配合物具有良好的荧光性质，Tb~(3+)配合物的荧光较强。
4．配体6-乙酰氨基皮考林酸(图3)及其稀土配合物的合成、表征和荧光性质的研究。研究表明，配体与稀土离子配合物的可能组成为：REL_3·4H_2O(RE=La~(3+)、Eu~(3+)、Gd~(3+)、Tb~(3+))，其中Eu~(3+)、Tb~(3+)配合物具有良好的荧光性质，尤其是Eu~(3+)的荧光较强。
5．配体N~2，N~6-二(苯基氨基甲酰)吡啶-2，6-二甲酰胺(图4)的合成、表征。在合成稀土配合物时由于反应条件控制和配位方式复杂的原因未得到纯的配合物，有待于进一步的研究。
It is well known that rare earth complexes have excellent optical, electrical and magnetic properties. In these complexes, the energy can be transmitted effectively from the organic ligands to the center lanthanide ions through the antenna effect. So, the design of the ligands' structure to obtain more effective transmission becomes the key in the field of luminescene. Recently lanthanide complexes with open-chain amide ligands have attracted much attention mainly because the ligands have the unusual molecular structures: flexible chain, changeable terminal group and high selectivity and coordination to lanthanide ions.
In this dissertation, three series of open-chain amide ligands and their lanthanide complexes have been synthesized and characterized in details with elemental analyses, molar conductance, spectra (infrared, ~1HNMR, MS). The luminescence properties of the complexes have been investigated. The dissertation includes five aspects:
1. A brief view of the research progress in a variety of luminescent materials of lanthanide complexes and the prospect of rare earth complexes' application in many fields.
2. Synthesis and characterization of the ligand N,N'-(1,3-phenylene)dipicolinamide (Fig 1) and its rare earth complexes. The results indicated that the composition of the complexes is [REL(NO_3)_2]NO_3·H_2O (RE = La~(3+)、Eu~(3+)、Gd~(3+)、Tb~(3+)、). In these complexes, the europium complex exhibited characteristic fluorescence of europiumion.
3. Synthesis and characterization of the ligand6-acetamido-N,N-diethylpicolinamide (Fig 2) and its rare earth complexes. The results indicated that the composition of the complexes is [REL_2(NO_3)_2] NO_3·H_2O (RE = La~(3+),Eu~(3+)、Tb~(3+)). In these complexes, the terbium complex exhibited characteristic fluorescence of terbium ion.
4. Synthesis and characterization of the ligand 6-acetamidopicolinic acid (Fig 3) and its rare earth complexes. The results indicated that the composition of the complexes is REL_3·4H_2O (RE = La~(3+)、Eu~(3+)、Gd~(3+)、Tb~(3+)). In these complexes, the europium complex exhibited characteristic fluorescence of europium ion.
5. Synthesis and characterization of the ligand N~2,N~6-bis(phenylcarbamoyl)pyridine-2,6-dicarboxamide(Fig 4).
引文
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