在聚砜侧链合成与键合双齿席夫碱配基及功能化聚砜-Tb(Ⅲ)离子配合物荧光发射性能初探

Synthesizing and Bonding Bidentate Schiff Base Ligand on Side Chain of Polysulfone and Preliminary Exploration of Luminescence Property of Functionalized Polysulfone-Tb( Ⅲ) Complexes

使氯甲基化聚砜(CMPSF)的氯甲基与乙醛酸(GA)的羧基发生酯化反应,将乙醛(AL)基团键合在聚砜侧链,制得改性聚砜PSF-AL;接着,又使3-氨基吡啶(AP)的伯氨基与PSF-AL的醛基发生席夫碱反应,在聚砜侧链合成与键合了具有特定结构的双齿席夫碱配基AA,从而获得了双齿席夫碱配基功能化聚砜PSF-AA,采用红外光谱(FTIR)和核磁共振氢谱(1H NMR)等技术手段对其结构进行了表征。以功能化聚砜PSF-AA为大分子配体,与Tb(Ⅲ)离子及Eu(Ⅲ)离子分别配位,制得了二元高分子-稀土配合物PSF-(AA)3-Tb(Ⅲ)和PSF-(AA)3-Eu(Ⅲ),初步探索了两种配合物的光致发光性能。重点研究了功能化聚砜PSF-AA的制备反应,考察与分析了主要因素对CMPSF与GA之间酯化反应的影响规律,优化了反应条件。CMPSF与GA之间的酯化反应属氯烷的亲核取代反应,实验结果表明,适宜的溶剂为极性较强的N,N-二甲基乙酰胺,75℃为适宜的反应温度。大分子配体PSF-AA对Eu(Ⅲ)离子不产生敏化作用,而对Tb(Ⅲ)离子的荧光发射则产生强烈的敏化作用,配合物PSF-(AA)3-Tb(Ⅲ)发射出较强的Tb(Ⅲ)离子的特征荧光,即表现出发射绿光的光致发光性能。

The esterification of chloromethylated polysulfone （CMPSF） with glyoxylic acid （GA） afforded aldehyde（AL） modified PSF-AL. Subsequent condensation of PSF-AL with 3-aminopyridine led to bidentate Schiff base ligand-functionalized PSF-AA. The chemical structure of PSF-AA was characterized by FTIR and ^1H NMR spectra. The binary polymer-rare earth complexes of PSF-（AA）3-Tb（ Ⅲ） and PSF-（AA）3-Eu（ Ⅲ ） were prepared and their photoluminescence properties were preliminarily explored. Optimized esterification between CMPSF and GA were performed in N, N-dimethylacetamide at 75 %. The macromolecular PSF-AA does not exhibit sensitization towards Eu （Ⅲ） ion, whereas PSF-AA can strongly sensitize the fluorescence emission of Tb（ Ⅲ） ion. The complex PSF-（AA） 3-Tb（ Ⅲ ） emits characteristic green fluorescence of Tb（ Ⅲ） ion.