树枝形分子1,2,4,5-四芳基苯的合成、荧光性质和电存储效应  

Synthesis, Flourescence Properties and Storage Effect of a Novel 1,2,4,5-Tetra(aryl)benzene Dendrimer

作　　者：杨铧[1] 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》2013年第1期184-189,共6页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.61178057)资助项目~~

摘　　要：采用钯催化条件下多位点Heck偶联反应,以芳香八碘代物1,2,4,5-四{4-[N,N-二(4-碘苯基)氨基]苯乙烯基}苯(TPAB-I)和4-(N,N-二苯基)氨基苯乙烯为反应物,合成了一种新型荧光树枝分子1,2,4,5-四{4-{N,N-二{4-[4-(N,N-二苯基氨基)苯乙烯基]苯基}氨基}苯乙烯基}苯(TPAB-TPA).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TPAB-TPA在甲苯、乙酸乙酯、四氢呋喃、二氯甲烷和N,N-二甲基甲酰胺(DMF)溶液中的最大荧光发射峰分别位于483,457,497,531,505 nm.量子产率分别为0.48,0.28,0.23,0.49,0.18,在二氯甲烷和四氢呋喃(THF)中的荧光寿命分别为1.48和1.53 ns.用循环伏安法测定TPAB-TPA的HOMO能级和LUMO能级分别为-5.16和-2.64 eV.制备了ITO/TPAB-TPA/Al三明治型电存储器件,ON/OFF电流比大于104,在1 V的读取电压下,持续时间达到1000 s.Through palladium-catalyzed Heck reaction, a novel fluorescent dentrimer 1,2,4,5-tetra{4-{N,N-di{4-[4-（N,V- diphenylamino）styryl]phenyl}amino}styryl}benzene （TPAB-TPA） was synthesized by aromatic octoiodine-substituted 1,2,4,5-tetra{4-[N,N-bis（4-iodophenyl）amino]styryl}benzene （TPAB-I） and N,N-diphenyl-4-vinylaniline. Its structure was characterized through IR, ^1H NMR, HRMS. A detailed spectroscopic study of the dendrimer TPAB-TPA, including absorp- tion, fluorescence emission, fluorescence lifetime and fluorescence quantum yield, was conducted. The maxima emission wavelengths of TPBA-TPA in toluene, ethyl acetate, THF, dichloromethane and DMF were at 483,457, 497, 531 and 505 nm, respectively. The absorption peaks of the dendrimer were at 400 nm in dichloromethane solution and at 405 nm in DMF solu- tion. The quantum yield was 0.48 （in toluene）, 0.28 （in ethyl acetate） and 0.49 （in dichloromethane）. The dendrimer possess high solubility in organic solvents and large Stoke＇s shift （3434-6168）. The fluorescence lifetime was 1.53 ns in THF and 1.48 ns in dichloromethane, The electrochemical properties of the dendrimer TPAB-TPA were explored by cyclic voltam- metry. Its HOMO energy level was --5.16 eV and LUMO energy level was --2.64 eV. An organic electrical memory device with the sandwich structure of indium-tin oxide （ITO）/TPAB-TPA/A1 was fabricated. The device exhibits a flash memory effect with a high ON/OFF current ratio nearly 104 and a long retention time above 103 S with a read voltage 1.0 V.

关 键 词：树枝分子 HECK反应 电存储效应 荧光性质 双稳态 

分 类 号：TQ323.5[化学工程—合成树脂塑料工业]