侧链键合水杨醛型双齿席夫碱配基的功能化聚砜的合成及其稀土离子配合物的光致发光性能

Syntheses of Functional Polysulfones with Bonding Salicylaldehyde-Type Bidentate Schiff Base Ligand on Side Chain and Luminescence Properties of Their Rare Earth Complexes

通过氯甲基化聚砜(CMPSF)与4-羟基水杨醛(HSA)的亲核取代反应,将水杨醛(SA)基团键合在聚砜侧链,制得改性聚砜PSF-SA;再经PSF-SA的醛基分别与苯胺(AN)和环己胺(CA)发生席夫碱反应,获得了两种侧链键合了水杨醛型双齿席夫碱配基的功能化聚砜PSF-SAN和PSF-SCA,产物的结构由红外光谱和核磁共振氢谱表征。以两种功能化聚砜为大分子配体,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,初步探索了配合物的光致发光性能。本文重点研究了功能化聚砜PSF-SAN和PSFSCA的制备反应,考察与分析了主要因素对CMPSF与HSA之间亲核取代反应的影响规律。结果表明,对于该亲核取代反应,适宜的溶剂为极性较强的N,N-二甲基乙酰胺,80℃为适宜的反应温度。大分子配体PSFSAN对Eu(Ⅲ)离子的荧光发射产生强烈的敏化作用,配合物PSF-(SAN)_3-Eu(Ⅲ)发射红光;大分子配体PSF-SCA对Tb(Ⅲ)离子的荧光发射也产生敏化作用,配合物PSF-(SCA)_3-Tb(Ⅲ)发射绿光。

Two bidentate Schiff base ligand-functionalized PSFs,PSF-SAN and PSF-SCA were synthesized by the substitution reaction under optimal conditions,i. e. in N,N-dimethylacetamide at 80 ℃ from chloromethylated polysulfone（ CMPSF） as starting material and the Schiff base reaction in turn. The chemical structures of products were characterized by FT IR and 1 H NMR techniques. Their binary polymer-rare earth（Tb（ Ⅲ） ion and Eu（ Ⅲ））ion complexes were prepared,and their photoluminescence properties were preliminarily explored. The PSF-SAN produces strong sensitization action towards Eu（ Ⅲ） ion, and the complex PSF-（SAN）3-Eu（ Ⅲ） emits red fluorescence. While the PSF-SCA produce sensitization action towards Tb（ Ⅲ） ion,and the complex PSF-（SCN）3-Tb（ Ⅲ） emits green fluorescence.