【作者】 杜立波；

【导师】 李亚明；

【作者基本信息】 大连理工大学 ， 应用化学， 2006， 硕士

【摘要】 有机电致发光材料全色动态显示中所需的蓝光材料,至今还没有得到很好的解决,三苯胺类化合物不但具有独特的光,电化学特性,而且其强的紫外-可见区域的吸收以及蓝色发光可以满足蓝色电致发光材料的要求。 本文以三苯胺为母体设计并通过Sandmeyer,Ullmann,Vilsme（?）haack,Witting等八步反应合成了十种含不同取代基的直线型三苯胺均二苯乙烯,V型双苯乙烯基三苯胺和Y型三苯乙烯基三苯胺电致发光材料,通过IR,MS,¹H-NMR等手段确证了其结构,用紫外吸收光谱,荧光光谱,循环伏安法（CV）等手段研究了它们的光电性能,分析了它们的电化学行为,讨论了取代基对紫外吸收光谱,荧光发射光谱和电化学性质的影响。 目标化合物的紫外-可见最大吸收波长在378～422nm之间（e>10⁴）。随溶剂极性的增大,紫外-可见吸收波长发生蓝移,荧光发射波长发生红移,荧光量子产率降低,在不同溶剂中受光激发时,含供电基团（如-N（CH₃）₂,-OCH₃）的化合物则发出441～476nm的强烈蓝色荧光。氰基取代的化合物发出505～557nm的黄绿色荧光;Y型化合物的荧光量子效率和荧光强度都要比V型化合物的低,这可能是由于随发色团数目的增多,扭曲的TICT发光态消耗较多激发能造成的。激发光能量都在3.44eV左右,说明只要较低的驱动电压就可使其发光。 化合物都含有三苯胺结构单元,在电场作用下易失去电子,形成胺离子自由基,使其具有良好的空穴传输性能。含有供电基团（-OCH₃）的化合物在电场作用下经历两个失单电子过程,形成两对氧化还原峰,而含有吸电基团（如 CN）的化合物则经历一个失单电子过程,形成一对氧化还原峰。 引入供电基团（如-N（CH₃）₂,-OCH₃）后,分子氧化电位降低,HOMO能量升高,电离势降低,化合物的带隙（E_g）减小,;引入吸电基团（如-CN）后,氧化电位升高,LUMO能量降低,电子亲和势增加。 计算得到化合物的带隙值E_g（opt.）在2.51～2.82eV,电离势（P_I）在5.41～5.82eV,电子亲和势（E_A）在2.69～3.62 eV。数据表明化合物具有较宽的带隙,有望成为优良的空穴高效注入和传输的有机电致发光材料。更多还原

【Abstract】 The bule emitting materials for electroluminescent device needed in OLED haven’t been resovled. The compounds based on triphenylamine not only have special photoelectric properties, but also have intense absorption in Uv-vis region indicating that they are suitable for bule electroluminescent materials.Ten linear-, V- and Y-shaped compounds based on triphenylamine with different substituents are designed and synthesized by Sandmeyer reaction;Ullmann reaction, Witting reaction, Vilsmeierreaction, and their structure are confirmed by MS, IR and ~1H-NMR. Their Photo-electricities are determined by UV-vis spectra, photoluminescent spectra, Cyclic Voltammetry. The electrochemistry behavior is analyzed;the influence of substituents on the properties of photo-electricity is systematically discussed.The wavelength of emission is red-shifted, while the absorption is blue-shifted with increasing solvents polarity. The absorption is ranged from 378 to 422 nm. The compounds with cyano-group exhibit intense yellow-green photoluminescence;other compounds exhibit intense blue photoluminescence. The fluorescence quantum efficiency and fluorescence intensity of the Y-shaped compounds are lower than V-shaped compounds. The exciting energy is 3.44 eV, indicating that low potential can drive these compounds to emitting light.The compounds based on triphenylamine have good hole-transporting property because they are easily ionized forming anion under electric field acting. The compounds with electron donor have two reversible redox processes in the cyclic voltammogram;while the compounds with electron acceptor only have one reversible redox process.The result indicates that HOMO level of compound is raised by electron-donating group (-N(CH3)2,-OCH3), the oxidative onset potentials, the band gap and the ionization potentials are decreased, while LUMO level is lowered by the electron-withdrawing group(-CN), the oxidative onset potentials and electron affinities are increased.Their band gaps (Eg), electron affinity (E_A) and ionization potentials (P_I) calculated are 2.51-2.82 eV, 2.69-3.62 eV and 5.41-5.82 eV, respectively, indicating that compounds are good candidates as electroluminescent materials with good hole-transporting property.更多还原