【作者】 胡晓曦；

【导师】 王德才； 吕龙； 张俊祥；

【作者基本信息】 南京工业大学 ， 生物化工， 2006， 硕士

【摘要】 有机发光器件具有与集成电路相匹配的直流低电压驱动的特性,与传统发光器件相比具有更低的能耗、更好的视角、更高的亮度、更快的反应时间,是一种在平板显示等方面较传统发光器件更具优势的新技术。自有机薄层电致发光现象发现以来人们业已发现了众多有机发光材料,芴类衍生物便是其中得到公认的性能优异、最具发展前景的一类。本文采用向三联(9,9-二苯基芴)的共轭主链和侧链引入强吸电子的氟原子的方法,合成了五个氟代三联芴化合物,并初步研究了它们的光电性能,为寻找新的芴类有机发光材料和电子传输材料提供了新的合成方向。本文首先以2,7-二溴芴为原料,通过4-位硝化、还原和重氮化氟化三步反应合成了4-氟-2,7-二溴芴。后者与2,7-二溴芴、2-溴芴作为起始化合物,分别经过9-位氧化、Grignard反应和Friedel-Crafts烷基化反应三步反应得到六个9,9-二芳基芴化合物。随后本文以其中三个9,9-二苯基芴化合物制备了相应的硼酸酯,通过Suzuki偶联反应,与上述溴代9,9-二芳基芴合成了三联(9,9-二苯基芴)和五个氟代三联芴化合物。本文实验制备中间体和终产物共27个,其中新化合物16个,包括11个中间体和5个终产物。所有中间体和终产物都分别通过红外、核磁氢谱、核磁碳谱、质谱和元素分析确证了结构,部分含氟化合物也得到了核磁氟谱的确证。紫外吸收光谱检测发现,五个氟代三联芴化合物在280~400 nm范围内均有较强的π→π*电子跃迁产生的紫外吸收,最大吸收波长与三联(9,9-二苯基芴)一样分布在340~350 nm之间;在10-7mol/L的THF溶液中,它们在360~500nm蓝绿光波段显示有极强的荧光发射,与三联(9,9-二苯基芴)相似,最大发射波长也分布在394~398 nm范围内。其中由4’-氟-9,9’,9’,9’’-四苯基-9,9’’-二(五氟苯基)-9H,9’H,9’’H- [2,2’;7’,2’’]三联芴制成的有机电致发光器件可发射峰值456nm的蓝色光。其起动电压约为6V,22.5V时发光亮度约为452cd/m2,是一种有效的有机电致发光材料。更多还原

【Abstract】 Compared with traditional light-emitting devices, organic light-emitting devices matched equally with integrate circuits in the performance of low direct current drive voltage can work in lower power and provide wider visual angle, higher brightness and shorter responding time. It is a new superior technology of flat-panel displays. The tremendous materials following the discovery of efficient electroluminescence in organic conjugated thin films have been found, and fluorene-basedπ-conjugated compounds now are generally regarded as the most promising candidates for OLEDsHere we synthesized five new fluorinated ter(9,9-diphenylfluorene)s by introducing electronegative fluorin to the conjugated or branched chain of ter(9,9- diphenyl- fluorene)s. Then we confirmed their structures and researched their perfor- mance of photoelectricity for indicating the tendency to find new fluorene-based organic light-emitting materials and electron transport materials.Firstly, 4-fluoro-2,7-dibromofluorene was synthesized from 2,7-dibromofluorene by 4-nitration, reduction, diazotization and fluorination. The former and 2,7-dibromo- fluorene, 2-bromofluorene were 9-oxidation, and then we attained six 9,9-diaryl- fluorene-based compounds by Grignard reaction and Friedel-Crafts reaction. We prepared the boracic esters of the three 9,9-diphenylfluorene-based compounds made by Friedel-Crafts reaction. Finally, we attained the ter(9,9-diphenylfluorene) and five new fluorinated ter(9,9-diphenylfluorene)s by Suzuki Coupling reaction. We prepared twenty-seven compounds in all and attained sixteen new compounds which included eleven intermediates and five products. The structures of all intermediates and products were confirmed by IR, 1HNMR, 13CNMR, MS and EA. Some fluoride were confirmed by 19FNMR.It is found that those five fluorinated ter(9,9-diphenyl-fluorene)s have strongπ→π* absorption in the region of 280~400nm. Their maximum absorption which are similar to ter(9,9-diphenylfluorene) distribute over 340nm to 350nm. They emitted strong blue-green fluorescence in solution of THF in the region of 360~500nm, and their maximum emission which distribute over 394nm to 398nm are same as ter(9,9-diphenylfluorene). The organic electroluminescent device made of 4’-fluoro-9,9’,9’,9’’-tetraphenyl-9,9’’-di(penta-更多还原