有机化学 ›› 2012, Vol. 32 ›› Issue (10): 1958-1964.DOI: 10.6023/cjoc1201141 上一篇    下一篇

研究简报

一种新型树枝分子的合成及其荧光性质

罗蔓利, 钱鹰   

  1. 东南大学化学化工学院 南京 211189
  • 收稿日期:2012-01-14 修回日期:2012-05-23 出版日期:2012-10-25 发布日期:2012-06-21
  • 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 and Fluorescence Properties of a Novel Dendrimer

Luo Manli, Qian Ying   

  1. School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189
  • Received:2012-01-14 Revised:2012-05-23 Online:2012-10-25 Published:2012-06-21
  • Supported by:

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

以芳香八碘代物1,2,4,5-四{4-[N,N-二(4-碘苯氨基)]苯乙烯基}苯(TPABI)和4-乙烯基吡啶在钯催化下进行多位点Heck反应, 制备得到一种新型荧光树枝分子1,2,4,5-四{4-[N,N-二(4-吡啶乙烯基)苯氨基]苯乙烯基}苯(TPABPy). 目标化合物的结构经过红外光谱、核磁共振谱、高分辨质谱确认. 树枝分子TPABPy在THF, 乙酸乙酯, 二氯甲烷, DMF, DMSO溶液中的最大发射波长分别为490, 493, 510, 536, 543 nm. Stoke’s位移分别为4717 (THF), 4969 (乙酸乙酯), 5330 (二氯甲烷), 6281 (DMF), 6398 (DMSO) cm-1. 在THF 和DMF中的荧光量子产率分别为0.87和0.72. 在THF和乙酸乙酯中的荧光寿命分别为1.29和1.77 ns. 研究了树枝分子TPABPy在不同pH值下的荧光行为, 在pH为2.41时荧光强度最大. 用循环伏安法测定了分子的前线轨道能级, HOMO轨道能级为-4.94 eV, LUMO轨道能级为-2.38 eV.

关键词: 荧光树枝分子, 多位点Heck反应, 溶剂效应, 荧光寿命, 前线轨道

Through palladium-catalyzed Heck reaction, a novel fluorescent dentrimer 1,2,4,5-tetra{4-[N,N-bis(4-pyridyl- vinyl)phenylamino]styryl}benzene (TPABPy) was synthesized by aromatic eight iodine-substituted 1,2,4,5-tetra{4-[N,N-bis- (4-iodinephenylamino)styryl]}benzene (TPABI) and 4-vinylpyridine. The dentrimer was characterized through IR, 1H NMR and HRMS techniques. The maxima emission wavelengths in THF, ethyl acetate, dichloromethane, DMF and DMSO were 490, 493, 510, 536 and 543 nm, respectively. Stoke’s shift was 4717 (THF), 4969 (ethyl acetate), 5330 (dichloromethane), 6281 (DMF), 6398 (DMSO) cm-1. The fluorescence lifetime for TPABPy was 1.29 ns with fluorescence quantum yield of 0.87 in THF. The fluorescent behavior of TPABPy in different pH was studied , and the fluorescent intensity maximum was in pH 2.41. The electrochemical properties were explored by cyclic voltammetry, the HOMO and LUMO energy levels of dentrimer were -4.94 and -2.38 eV, respectively.

Key words: fluorescent dentrimer, Heck reaction, solvent effect, fluorescent lifetimes, frontier orbital