吡啶-2,6-二甲酰腙类化合物及其Tb(Ⅲ)和Eu(Ⅲ)配合物的合成与荧光性能

吡啶-2,6-二甲酸经酯化,肼解得吡啶-2,6-二甲酰肼(2),(2)与芳香醛缩合得到了3个新的酰腙配体:吡啶-2,6-二甲酰肼苯甲醛腙(3a)、吡啶-2,6-二甲酰肼水杨醛腙(3b)和吡啶-2,6-二甲酰肼呋喃甲醛腙(3c),其结构经元素分析、IR、1HNMR和MS进行了确认。制备了吡啶-2,6-二甲酰肼与这三种新型配体的Tb(III)和Eu(III)配合物,并对配合物的溶液态的荧光性质进行了研究。结果表明,吡啶-2,6-二甲酰肼苯甲醛腙(3a)和吡啶-2,6-二甲酰水杨醛腙(3b)作为荧光敏化剂,对Eu3+和Tb3+的荧光敏化性能比吡啶-2,6-二甲酰肼以及大多数吡啶-2,6-二甲酸衍生物要好,是较理想的稀土荧光敏化剂,它们的稀土配合物在分子偶极矩较小的溶剂中荧光强度较强。

Syntheses and Fluorescence Properties of Tb(Ⅲ) and Eu(Ⅲ) Complexes with Pyridine-2,6-dimethylhydrazones

Three novel pyridine-2,6-dimethylhydrazones were synthesized by condensation of pyridine-2,6-dimethylhydrazines from pyridine-2,6-dicarboxylic acid with various aromatic aldehydes and were characterized by elemental analysis,IR,1HNMR and MS,The Tb3+ and Eu3+ complexes of pyridine-2,6-dimethylhydrazine and three pyridine-2,6-dimethylhydrazones were obtained and their fluorescence intensities were analyzed.The results show that the fluorescence intensities of pyridine-2,6-dimethylhydrazones of 2-hydroxy benzaldehyde and benzaldehyde are stronger than most pyridine-2,6-dicarboxylic acid derivatives and pyridine-2,6-dimethylhydrazine.The fluorescence of the complexes in low-polar solvent is better than that in high-polar solvent,they are better sensitizers of Tb(Ⅲ) and Eu(Ⅲ).