通过轴向配位反应实现4-乙烯基吡啶聚合物的卟啉功能化

通过轴向配位反应,将四苯基卟啉锌(ZnTPP)键合在4-乙烯基吡啶(4VP)与苯乙烯(St)共聚物P(4VP-co-St)的侧链,制得了卟啉功能化的大分子ZnTPP-P(4VP-co-St).通过FTIR与1H-NMR对其化学结构进行了表征,重点研究了时间、温度对轴配过程的影响,以及大分子轴配化合物ZnTPP-P(4VP-co-St)的谱学性能,对其光物理行为进行了较为深入的分析.研究结果表明,以共聚物P(4VP-co-St)的吡啶侧基为配体,通过轴向配位反应可顺利地制备卟啉功能化的大分子ZnTPP-P(4VP-co-St),且温度越低,键合量越大.该大分子具有类似于ZnTPP的特征电子吸收光谱与荧光发射光谱,同时也显示出轴向配位的特征.与小分子ZnTPP相比,ZnTPP-P(4VP-co-St)的吸收光谱和发射光谱都发生了明显的红移.大分子轴配化合物ZnTPP-P(4VP-co-St)的光物理行为也呈现出一定程度的高分子效应,随着大分子链中ZnTPP键合量的增大,相近的ZnTPP侧链单元之间会发生能量转移,使荧光发射强度有所减弱.

PORPHYRIN FUNCTIONALIZING OF 4-VINYLPYRIDINE POLYMERS VIA AXIAL COORDINATION REACTION

Zinc tetraphenylporphyrin (ZnTPP) was bound on the side chains of the copolymers of 4-vinylpyridine and styrene (P(4VP-co-St)) via axial coordination reaction,and the porphyrin-functionalized polymer ZnTPP-P(4VP-co-St) was prepared.The structures of ZnTPP-P(4VP-co-St) were characterized with FTIR and ¹H-NMR spectra.The effects of time and temperature on the bonding degree of ZnTPP on P(4VP-co-St) were analyzed.Moreover,the electronic absorption and fluorescence emission spectra of ZnTPP-P(4VP-co-St) were mainly studied,and its photo-physical behaviors were described in depth.The experimental results show that the porphyrin-functionalized macromolecules ZnTPP-P(4VP-co-St) can be favorably prepared through the axial coordination reaction between the side pyridine groups of the copolymer P(4VP-co-St) and the metalloporphyrin ZnTPP,and the lower the temperature,the higher the bonding degree of ZnTPP is.The macromolecular axial coordination compound ZnTPP-P(4VP-co-St) possesses the characteristic electronic absorption and fluorescence emission spectra of ZnTPP,and at the same time,it exhibits the characters of axial coordination compounds.As compared with the small molecular ZnTPP,all of the absorption and emission spectra of ZnTPP-P(4VP-co-St) exhibit obvious red shift.In addition,the behavior of the axial coordination compound ZnTPP-P(4VP-co-St) exhibits a polymer effect in its photophysical behavior.As the bound amount of ZnTPP on the side chain of polymer P(4VP-co-St) is increased,the energy transfer between the adjacent side ZnTPP units will be produced,resulting in the slight weakening of the fluorescence emission.