一种9-苯基芴位阻功能化的苯胺中间体的设计合成、表征及其光电性质

以醋酸为溶剂、浓硫酸为催化剂在120 ℃回流24 h, 通过傅克反应设计合成了一种大体积位阻型9,9-二芳基芴中间体9-(4-苯胺基)-9-苯基芴](FPPhNH₂)。通过核磁氢谱、质谱、红外等方法对该化合物的分子结构进行了详细表征。核磁氢谱和红外光谱分别在6.55 ppm，3 481和3 385 cm-1显示该化合物的特征官能团-氨基。用紫外-可见光谱和荧光光谱对9-(4-苯胺基)-9-苯基芴的光学性质进行了表征和初步探讨。研究结果表明, 具有大体积空间位阻效应的9-(4-苯胺基)-9-苯基芴在二氯甲烷溶液中有四个主要吸收峰, 其吸收波长分别为243，257，298和311 nm; 在波长为308 nm的谱激发下，得到发射波长为300～500 nm的发射光谱曲线, 其荧光光谱最大发射波长为328 nm, 且在405 nm左右有一个细小的峰并有一个长的拖尾至500 nm, 这可能源于苯胺基团中分子间氢键所引起的。恰当的荧光发射范围(300～500 nm), 使其能够和经典蓝光客体材料双(4,6-二氟基吡啶-N,C2)吡啶甲酰合铱(FIrpic)的吸收光谱有较大的重叠(300～500 nm)。通过巧妙的分子裁剪, 或可得性能优异的主体材料, 进而使制备高性能的发光器件成为可能。为了进一步了解该化合物的光电性能, 以乙腈为溶剂, 以四丁基六氟磷酸胺为电解质, 通过循环伏安法对该化合物的电化学性能进行了表征。其起始氧化电位和还原电位分别为0.898和-0.759 V, HOMO和LUMO能级分别为-5.38和-3.72 eV, 其较高的HOMO能级和较低的LUMO能级有利于空穴和电子的注入/传输, 这将进一步优化成性能优异的主体材料, 并为进一步制备性能优异的有机半导体发光器件提供有益参考。

The Design,Synthesis,Characteristics and Photoelectric Properties Research of A Bulky Steric Hindrance 9-Phenyl-Fluorene Functionalized Aniline Intermediate

In this paper ,with sulfuric acid as a catalyst and acetic acid as solution at the temperature of 120 ℃ and refluxing peri‐od for 24 hours ,a sterically hindered bulky 9 ,9‐diarylfluorene intermediate of 9‐(4‐anilino)‐9‐phenyl‐fluorene] had been suc‐cessfully designed and synthesized with Friedel‐Crafts reaction .The molecular structure of this compound was characterized in detail with nuclear magnetic resonance hydrogen spectrum ,mass spectrometry ,infrared ray ,and so on .Nuclear magnetic reso‐nance hydrogen spectrum and infrared ray spectrum of the compound indicated that the characteristic functional group amino of the compound at 6.55 ppm ,3 481 and 3 385 cm-1 ,respectively .UV‐visible and fluorescence spectra properties of 9‐(4‐anilino)‐9‐phenyl‐fluorene were characterized and discussed preliminarily ,respectively .The research results show that the 9‐(4‐anilino)‐9‐phenyl‐fluorene with bulky steric hindrance effects has four main absorption peaks with wavelength of 243 ,257 ,298 and 311 nm in dichloromethane solution ,respectively .Moreover ,with the excitation wavelength of 308 nm ,an emission spectrum curve was obtained with wavelength of 300~500 nm ,which has the maximum emission peak of 328 nm with a slim peak at about 405 nm and a long tail to 500 nm .The long tail was probably attributed to the interaction of intermolecular hydrogen bonding from aniline .The appropriate scope of fluorescence emission (300~500 nm) make the compound overlap with the absorption spectra of the classic blue material Bis(3 ,5‐difluoro‐2‐(2‐pyridyl)phenyl‐(2‐carboxypyridyl)iridium (Ⅲ) (FIrpic) (300~500 nm) .It is possible to obtain excellent host materials through proper molecular tailoring and prepare well for high performance light‐emitting device .In order to further understand the photoelectric properties of the compound ,we used acetonitrile as solvent and tetrabu‐tylammonium hexafluorophosphate as electrolyte ,and the electrochemical properties of the compound was characterized with cy‐clic voltammetry measurements .The onset of the reduction and oxidation potential of the compound are -0.759 and 0.898 V , and the corresponding HOMO and LUMO energy levels are -5.38 and -3.72 eV ,which wolud be beneficial to holes and elec‐trons injection/transportation and further modified to be excellent host materials .All of these data would provide a useful refer‐ence for further fabrication of organic semiconductor luminescent device with high performance .