有机化学 ›› 2014, Vol. 34 ›› Issue (3): 537-545.DOI: 10.6023/cjoc201309005 上一篇    下一篇

研究论文

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

管成飞, 钱鹰   

  1. 东南大学化学化工学院 南京 211189
  • 收稿日期:2013-09-03 修回日期:2013-10-27 出版日期:2014-03-25 发布日期:2013-11-20
  • 通讯作者: 钱鹰 E-mail:yingqian@seu.edu.cn
  • 基金资助:

    国家自然科学基金(No. 61178057)资助项目.

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

Guan Chengfei, Qian Ying   

  1. School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189
  • Received:2013-09-03 Revised:2013-10-27 Online:2014-03-25 Published:2013-11-20
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 61178057).

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-[NN-二(4-吡啶乙烯基)苯基]氨基}苯乙烯基}蒽(4Py-PAA)和9,10-二{4-{4-[NN-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.

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

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 solvent 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.

Key words: Heck reaction, pyridine substituent, 9,10-diaryl anthracene, aggregation-induced emission enhancement, solvatochromic behavior, two-photon induced fluorescence