【作者】 刘伟；

【导师】 刘建辉；

【作者基本信息】 大连理工大学 ， 物理化学， 2005， 硕士

【摘要】 本文介绍了电致发光材料特别是金属络合物类电致发光材料的研究进展并在此基础上设计合成了两个分别以双炔噻吩和双炔为桥基的双核钌联吡啶电致发光材料8a和8b,其中8a未见文献报道,其结构通过质谱、核磁共振氢谱、元素分析等手段进行了表征。并对8a和8b的光物理、电化学和电化学发光（BCL）等性能进行了分析测试。 1) 以2,2’-联吡啶为起始原料,经氧化,硝化,溴化反应得到4-溴-2,2’-联吡啶;经氧化,硝化,还原,重氮化,碘化反应合成了4-碘-2,2’-联吡啶,总产率分别为27%和32%;通过改进硝化和溴化的试验条件,提高了该步骤的产率;讨论了硝化和重氮化反应机理。 2) 以2,5-二碘噻吩,三甲基硅乙炔,4-溴-2,2’-联吡啶和4-碘-2,2’-联吡啶为原料,经过连续两次的钯催化偶合反应,在与Ru（bpy）₂²⁺Cl₂^-·2H₂O反应得到化合物8a和8b,总产率分别为76%和78%;将4-碘-2,2’-联吡啶用于Sonogashira偶合反应,并对该反应的反应条件进行了探索,对反应机理进行了讨论。 3) 对8a和8b的紫外-可见光谱、激发-发射光谱、电化学性质（循环伏安法）、电化学发光性质进行了测试。发现由于噻吩的嵌入,8a的最大吸收波长和最大发射波长相对于8b分别红移了6nm和5nm,且8a的摩尔消光系数大于8b。8a和8b的循环伏安法的氧化还原电位表现出对称双核三联吡啶钌络合物的基本特征,半波电位基本相等;首次将噻吩桥类双核钌联吡啶络合物用于电化学发光研究,发现在恒定电位激发下,8a和8b的ECL强度是基准物三联吡啶合钌的3.5-4倍,8a强于8b,而脉冲电位激发下,8a的ECL强度约为三联吡啶合钌的40倍;并对双核钌联吡啶络和物的ECL发光机理进行了探讨。更多还原

【Abstract】 According to the research progress of electroluminescent materials specially on metal complexes, two kinds of binusclear ruthenium（II） electroluminescent materials 8a and 8b with diethynyl-thiophene and diethynyl bridged were designed and synthesized. The former is novel and the latter is known. The structure of 8a and 8b were characterized by API-MS, ’H-NMR, Elemental Analysis. Their photophysical, electrochemical and ECL properties were studied by UV-vis,fluorescence spectra, cyclic voltammetry and ECL analysis.1) By using 2, 2’-bipyridine as starting material, 4-bromo-2, 2’-bipyridine was obtained through oxidation, nitration and bromination and 4-iodo-2,2’-bipyridine was obtained through oxidation, nitratio, reduction, diazotization and iodination, with total yield of 27% and 32% respectively. The yields were effectively increased by the modification of nitration and bromation. The mechanisms of nitration and diazotization were discussed.2) By using 2,5-diiodothiophene, trimethylsilylacetylene, 4-bromo-2, 2’-bipyridine and 4-iodo-2,2’-bipyridine as starting materials, 8a and 8b were obtained with total yield of 76% and 77% respectively through repeated Pd-catalyzed coupling reaction, then coordinated with cis-Ru（bpy）₂²+Cl2^-2H₂O. Compound 4-iodo-2,2’-bipyridine was applied for the Sonogashira reaction, the reaction condition was studied and the mechanism of Sonogashira reaction was discussed.3) The photophysical, electrochemical, electroluminescence properties of binuclear Ruthenium complexes 8a and 8b were studied. Compared to 8b, the maximum absorption of 8a has 6nm of red shift, while maximum emission has 5nm of red shift. On the other hand, molar absorption coefficient was increased for the same reason. The cyclic voltammogram of 8a and 8b showed the feature which were characteristic for ruthenium（H） tris-bipyridyl species. The redox potentials of 8a are nearly equaled to those of 8b. The ECL of 8a and 8b were 3.5-4 times larger than Ru（bpy）3²+in canstant voltage and 40 times larger in pulse voltage. The mechanism of ECL was discussed.更多还原