糠醛缩胺型高分子-稀土发光配合物的制备及发光特性

Luminous properties of furfural/amine type rare-earth polymer complexes

通过三步大分子反应法,制备了糠醛缩苯胺型席夫碱功能聚砜和糠醛缩环己胺型席夫碱功能化聚砜。首先,通过傅克烷基化反应在聚砜(PSF)侧链键合氯甲基,制备氯甲基化聚砜CMPSF;以制备的氯甲基化聚砜为亲电试剂,与糠醛(FF)发生傅克烷基化反应,制备侧链键合有糠醛基团的功能化聚砜PSF-FF;使糠醛的醛基分别与苯胺(AN)和环己胺(CA)的氨基发生席夫碱反应,制备糠醛缩苯胺型席夫碱功能聚砜PSF-FA和糠醛缩环己胺型席夫碱功能化聚砜PSF-FC。用红外光谱(FTIR)和核磁共振氢谱(IHNMR)表征功能化聚砜的结构。在此基础上,以这两种功能化聚砜为大分子配体,分别与Eu(Ⅲ)离子和Tb(Ⅲ)离子进行配位,制备了二元配合物PSF-(FA)3-Eu(Ⅲ)、PSF-(FA)3-Tb(Ⅲ)和PSF-(FC)3-Eu(Ⅲ)、PSF-(FC)3-Tb(Ⅲ),初步探索了配合物的光致发光性能。重点研究了制备糠醛缩胺型功能化聚砜PSF-FA和PSF-FC的反应,考察分析了主要因素对CMPSF与FF之间傅克烷基化反应(属亲电取代反应)的影响规律。结果表明,对于该傅克烷基化反应,N,N-二甲基乙酰胺因极性较强为适宜的溶剂,反应适宜的温度为70℃。二元配合物PSF-(FA)3-Eu(Ⅲ)发射Eu(Ⅲ)离子特征荧光(红光),即大分子配体PSF-FA可敏化Eu(Ⅲ)离子的荧光发射,而PSF-(FA)_3-Tb(Ⅲ)无明显的荧光效果,大分子配体PSF-FA的三重态能级与Eu(Ⅲ)离子共振能级比较匹配;配合物PSF-(FC)3-Tb(Ⅲ)发射Tb(Ⅲ)离子的特征荧光(绿光),即大分子配体PSF-FC可敏化Tb(Ⅲ)离子的荧光发射,而PSF-(FA)_3-Eu(Ⅲ)无明显的荧光效果,大分子配体PSF-FC的三重态能级与Tb(Ⅲ)离子共振能级比较匹配。

By using three steps of macromolecular reaction,furfural/anil type Schiff base functional polysulfone and furfural/cyclo-hexylamine type Schiff base functional polysulfone were prepared.First,chloromethylation polysulfone CMPSF were prepared by Friedel-crafts alkylation reaction between polysulfone(PSF)and1,4-Bis(chloromethoxy)butane(BCMB),bonding methyl chloride in the side chain of PSF;Then,the CMPSF as electrophilic reagent,has a Friedel-crafts alkylation reaction with furfural(FF).Functional polysulfone PSF-FF were successfully made,side chain of which bonded with furfural groups FF;Finally,the aldehyde group of PSF-FF respectively react with aminos of aniline(AN)and cyclohexylamine(CA),furfural/anil type Schiff base functional polysulfone PSF-FA and furfural/cyclohexylamine type Schiff base functional polysul-fone PSF-FC were successfully synthesized.The structures of the functional polysulfones were characterized by FTIR^H-NMR.On this basis,the two kinds of functional polysulfone as macromolecular ligand,respectively coordinated with Eu(IH)ion and Tb(IH)ion,the binary complexes PSF-(FA)3-Eu(IH),PSF-(FA)3-Tb(IH)and PSF-(FC)3-Eu(IH),PSF-(FC)3-Tb(IH)were prepared.The photoluminescence properties of complexes were preliminary explored.This study ismainly focused on the reaction of preparation of furfural/amine type functional polysulfone PSF-FA and PSF-FC,So the main factors impact on Friedel-crafts alkylation reaction(belong to electrophilic reaction)between CMPSF and FF was analyzed.The re-sults show that,for the Friedel-crafts alkylation reaction,DMAC is the appropriate solvent due to its strong polarity,the appropriate temperature is70.Binary complex PSF-(FA)3-Eu(IH)emits characteristic fluorescence of Eu(IH)ion(red light),indicating themacromolecular ligand PSF-FA can sensitize the fluorescence emission of Eu(IH)ion,the complex PSF-(FA)3-Tb(IH)has no ob-vious fluorescence,triplet energy level of macromolecular ligand PSF-FA matches with resonance level of Eu(IH)ion;The complex PSF-(FC)3-Tb(HI)emits the characteristics fluorescence of Tb(IH)ion(green lighe),indicating the macromolecular ligand PSF-FC can sensitize the fluorescence emission of Tb(HI)ion,and the complex PSF-(FC)3-Eu(HI)has no obvious fluorescence,triplet energy level of macromolecular ligand PSF-FC matches with resonance level of Tb(IH)ion.