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通过Sonogashira偶联反应制备了含有4-[2-(对苯胺)乙烯基]苯(M1)、2,5-二戊烷氧基-1,4-二乙炔基苯(M2)和9-辛基咔唑(M3)3种结构单元的三元共轭聚合物PPEC,并通过核磁共振氢谱确定了3种结构单元的比例为0.54∶1.00∶0.46(M1∶M2∶M3).由于在PPEC的侧链中含有氨基基团,通过在PPEC的THF溶液中分别加入水、甲醇和正己烷,诱导其产生聚集,其聚集后的荧光性质表现出明显的不同,在THF与水的混合溶剂中,PPEC发光强度会随着水含量的增加先是急剧降低,而后在高水含量时发光强度又显著增强;在THF与甲醇的混合溶剂中,PPEC发光强度随着甲醇的加入只是逐渐降低;在THF与正己烷的混合溶剂中,PPEC的发光强度则会随着正己烷的增加而增强.该结果表明氨基通过与水,或者自身所形成氢键作用,改变了PPEC分子链之间的聚集态结构,降低了分子内旋转非辐射能量效率,从而有效改善共轭聚合物的主链发光性质,这为设计聚集态下(或固态下)高性能的荧光共轭聚合物提供了一种新思路.
A solution containing 4- [2- (p-anilino) vinyl] benzene (M1), 2,5-dipentanoxy-1,4-diethynylbenzene (M2) and 9-octyl (M3) three kinds of structural units ternary conjugated polymer PPEC, and by nuclear magnetic resonance spectroscopy to determine the three structural units ratio of 0.54: 1.00: 0.46 (M1: M2: M3) Of the side chain containing amino groups, by adding water, methanol and n-hexane were added to the solution of PPEC in THF to induce their aggregation, the fluorescence properties after aggregation showed a clear difference, in a mixed solvent of THF and water , The luminescence intensity of PPEC firstly decreases sharply with the increase of water content, and then increases significantly at high water content. In the mixed solvent of THF and methanol, the luminescence intensity of PPEC decreases with the addition of methanol; in THF And n-hexane, the emission intensity of PPEC increases with the increase of n-hexane, which shows that the amino group changes the aggregated structure between PPEC molecular chains through the hydrogen bond with water or itself , Reducing the intramolecular rotational non-radiative energy efficiency, thereby effectively improving the main conjugated polymer Chain luminescence properties, which provides a new idea for the design of aggregated (or solid state) high-performance fluorescent conjugated polymers.