含吡啶端基9,10-双芳基蒽共轭分子的合成、聚集诱导荧光增强及双光子诱导荧光  

Synthesis,Aggregation-Induced Emission Enhancement and Two-Photon Induced Fluorescence of Pyridine End-Capped 9,10-Diaryl Anthracene

作　　者：管成飞 钱鹰[1] 

机构地区：[1]东南大学化学化工学院,南京211189

出　　处：《有机化学》2014年第3期537-545,共9页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.61178057)资助项目~~

摘　　要：通过Heck反应合成了2个以吡啶为端基的9,10-双芳基蒽共轭分子9,10-二{4-{4-[N,N-二(4-吡啶乙烯基)苯基]氨基}苯乙烯基}蒽(4Py-PAA)和9,10-二{4-{4-[N,N-二(2-吡啶乙烯基)苯基]氨基}苯乙烯基}蒽(2Py-PAA),化合物结构经过1H NMR,13C NMR,HRMS-MALDI-TOF确证.测定了化合物在不同极性溶剂中的紫外吸收光谱、荧光光谱、荧光寿命及量子产率,测算了4Py-PAA和2Py-PAA的偶极矩.通过循环伏安法研究了它们的前线轨道能级.测定了4Py-PAA和2Py-PAA的固体荧光光谱、固体荧光量子产率及在不同含水量的水/THF混合溶液中的荧光光谱.实验发现4Py-PAA在THF溶液中发出蓝绿色荧光,固体时发出红色荧光,在含水量为70%的水/THF混合溶剂中发出黄色荧光,荧光强度是纯四氢呋喃(THF)的3倍,呈现聚集荧光增强性质.在800 nm飞秒激光下采用双光子诱导荧光参比法测定了4Py-PAA和2Py-PAA在THF溶液中的双光子吸收截面分别为193和101 GM.实验结果表明含有2位和4位吡啶端基9,10-双芳基蒽共轭分子具有良好的荧光发射性能及双光子吸收性质.New dendrimers 9,10-bis {4-[N,N-bis（4-pyridylvinyl）phenylamino]styryl } anthracene （4Py-PAA） and 9,10-bis {4- [N,N-bis（2-pyridylvinyl）phenylamino]styryl}anthracene （2Py-PAA） were synthesized by Heck coupling reaction with pyridine as branches, and anthracene as the core. The structures were characterized by 1H NMR, 13C NMR, HRMS-MALDI-TOF. The UV-vis spectra, fluorescence spectra, fluorescence lifetime and quantum yields were measured, and dipole moments of 4Py-PAA and 2Py-PAA were calculated. The frontier orbitals were studied by cyclic voltammetry. Solid fluorescence spectra, fluorescence spectra in aqueous tetrahydrofuran （THF） with different water/THF ratios and absolute quantum yield of 4Py-PAA and 2Py-PAA were measured. 4Py-PAA emitted blue-green light in THF and red light in the solid state. In the sol- vent mixture with 70% water, 4Py-PAA emitted a yellow light and the intensity was 3-fold higher than that in THF. Therefore, 4Py-PAA is AIEE-active. Measured with the two-photon induced fluorescence method, the values of TPA cross-section of 4Py-PAA and 2Py-PAA in THF were 193 and 101 GM, which obtained at 800 nm wavelength from a femtosecond laser source. The results showed that 9,10-diaryl anthracene end-capped with 2-pyridine and 4-pyridine had good fluorescence and two-photon absorption properties.

关 键 词：HECK反应 吡啶取代基 9 10 双芳基蒽 聚集荧光增强 溶剂效应 双光子诱导荧光 

分 类 号：TQ253.2[化学工程—有机化工] O657.3[理学—分析化学]