新型磷光铱（Ⅲ）配合物的合成及性质研究

发布时间：2018-05-14 05:02

本文选题：铱配合物 + 2-苯基吡啶　；参考：《云南师范大学》2017年硕士论文

【摘要】：磷光三价铱配合物作为有机发光材料被人们广泛研究,在于其具有发光效率高,磷光寿命短,发光颜色可调等优势。这样的三价铱配合物由于其中心原子铱的d轨道上存在强的自旋轨道耦合,使得单重态和三重态混合,原来禁阻的三线激发态至基态的跃迁,由于系间窜越作用变得允许。最近几年,关于铱配合物的研究,主要是通过设计合成新型配体,改变配体上的取代基团及取代位置等方式来合成新型的铱配合物从而调节其发光波长,提高色纯度和提高发光效率,并取得了显著成效。因此设计合成新型结构的铱配合物,对开发高效、多样的有机电致发光材料具有深远的意义。论文设计合成了以含有S=O和C=O螯合位点的2-(苯磺酰基)苯乙酮(2-(phenylsulfonyl)acetophenone,PSAP)、2-(对甲苯磺酰基)苯乙酮(2-(p-toluenesulfonyl)acetophenone,TSAP)和含有P=O和C=O螯合位点的N-(1,3-二甲基-2-氧代-1,3,2-二氮杂磷杂环己烷)苯甲酰胺(N-(1,3-dimethyl-2-oxido-1,3,2-diazaphosphinan-2-yl)benzamide,DAPB)为辅助配体,以强吸电子基团-F和-CF3取代的2-苯基吡啶衍生物2-(2,4-二氟苯基)吡啶(2-(2,4-difluorophenyl)pyridine,dfppy)、2-(4-三氟甲基苯基)吡啶(2-(4-trifluoromethylphenyl)pyridine,tfmppy)、2-(2-氟-4-三氟甲基苯基)吡啶(2-(2-fluoro-4-trifluoromethylphenyl)pyridine,ftfmppy)为主配体,合成两类新型的铱配合物。通过核磁共振、红外光谱和质谱对配合物进行鉴定和表征,确定结构与预测结构相同。测定他们的光物理性质和电化学性质。测试结果表明配合物的能级间隙在2.48-2.82 eV之间,在二氯甲烷溶液中的发射波长为479-517 nm,固体发射波长为502-544 nm,配合物的发光量子效率为6.3-51.1%。主配体相同时PSAP和TSAP为辅助配体的配合物具有较高的荧光量子效率,以DAPB为辅助配体的配合物的发射波长较长,与Ir(C^N)3构型配合物相比,本文报道的两类辅助配体合成的Ir(C^N)2(L^X)构型配合物具有更高的发光效率。由于PSAP和TSAP为辅助配体的配合物的发光效率较高,稳定性较好,因此将该类配合物的固体粉末用于制备蓝光InGaN为基底的发光二极管,测试其发光致发光性能。二极管的发射波长在507-543 nm之间,色坐标显示它们的发光在蓝绿光和黄绿光区域。其中配合物(ftfmppy)2Ir(TSAP)的发光效率最高为5.6lm/W,配合物(dfppy)2Ir(PSAP)的色坐标为(0.316,0.431),发光区域与白光最接近。
[Abstract]:Phosphotrivalent iridium complexes have been widely studied as organic luminescent materials because of their advantages such as high luminescence efficiency, short phosphorescence lifetime and tunable luminescence color. Due to the strong spin-orbit coupling in the d-orbit of the iridium atom in the center of the iridium complex, the transition from the excited three-wire state to the ground state, which was originally forbidden, is allowed due to the intersystem crossover between the singlet and triplet states, and the transition from the excited state to the ground state of the trivalent iridium complex is permitted. In recent years, studies on iridium complexes have been focused on the synthesis of novel iridium complexes by designing and synthesizing new ligands, changing the substituents on ligands and changing their substituent positions to regulate their luminescence wavelengths. The color purity and luminous efficiency were improved, and remarkable results were obtained. Therefore, the design and synthesis of new iridium complexes have profound significance for the development of efficient and diverse organic electroluminescent materials. In this paper, 2-( phenylsulfonyl) acetophenone (2-phenylsulfonyl) acetophenone 2-( p-toluenesulfonyl) acetophenylacetophenone (p-toluenesulfonylacetophenone TSAP) and N-Poluenesulfonylacetophenone TSAP (containing the chelating sites of Po and Con O) have been designed and synthesized, and N-TSAP containing Po and Cno chelating sites have been designed and synthesized by using 2-phenylsulfonylacetophenylacetophenone TSAP (2-phenylsulfonylacetophenone TSAP) and N-trichlorobenzene 3- dimethyl-2-diazaphosphoryl heterocyclohexane (diazaphane) benzoyl cyclohexane. N-dimethyl-3-dimethyl-2-oxido-1 (2-diazaphosphinan-2-ylphosphinan-2-ylbenzamide-DAPB) was used as an auxiliary ligand. Two new iridium complexes were synthesized from 2-fluoro-2-fluoro-4- difluorophenylpyridyl 4-diophenylpyridine pyridine 4-diphenyl-pyridine 4-trifluoromethylphenyl) pyridine 4-trifluoromethylphenylpyridine 2-fluorine-4fluoromethylphenylpyridine 2-fluoro-4- trifluoromethylphenyl) pyridine 2-fluoro-4-trifluoromethylphenylpyridyl pyridine pyridineffftmppy2 (2-fluoro-4-trifluoromethylphenylpyridyl pyridine pyridineffftmppy2). The complex was characterized by NMR, IR and MS, and the structure was the same as the predicted structure. Their photophysical and electrochemical properties were measured. The experimental results show that the energy level gap of the complexes is between 2.48-2.82 EV, the emission wavelength in dichloromethane solution is 479-517 nm, and the solid emission wavelength is 502-544 nm. The luminescent quantum efficiency of the complexes is 6.3-51.1 nm. When the principal ligands are the same, the complexes of PSAP and TSAP as auxiliary ligands have higher fluorescence quantum efficiency, and the emission wavelengths of the complexes with DAPB as auxiliary ligands are longer than those of Ir(C ^ N3 complexes. In this paper, we report that the two kinds of auxiliary ligands have higher luminescence efficiency than the other two kinds of Ir(C ~ (2 +) -N ~ (2 +) -N ~ (2 +) -L ~ (2 +) complexes. Because of the high luminescence efficiency and good stability of the complexes with PSAP and TSAP as auxiliary ligands, the solid powders of these complexes were used to prepare blue light emitting diodes based on InGaN, and their luminescent properties were tested. The emission wavelengths of the diodes are between 507-543 nm. The color coordinates show their luminescence in the blue and yellow green regions. The luminescence efficiency of the complex is 5.6lm / W.The color coordinate of the complex is 0.3160.431g, and the luminescence region is the closest to the white light.
【学位授予单位】：云南师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4;TQ422

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