【作者】 宋阳；

【导师】 郑昌戈；

【作者基本信息】 江南大学 ， 应用化学， 2011， 硕士

【摘要】 2,2′-联吡啶及其衍生物和过渡金属有着较强的配合能力,这些配体及其配合物已经得到广泛的研究及应用。配体上电子结构与配合物的光电性质有着密切联系,因此对配体芳香环上的取代基的研究也就越来越受到关注。本文从2,2′-联吡啶出发,合成了一系列具有不同取代基的4,4′-二取代-2,2′-联吡啶衍生物及其与钌(II)的配合物,并对其性质及晶体结构进行了研究。以2,2′-联吡啶为起始原料,经N-氧化、硝化、卤代、脱氧及硅化等反应步骤合成得到了一系列4,4′二取代的2,2′-联吡啶衍生物:4,4′-二溴-2,2′-联吡啶、4,4′-二甲氧基-2,2′-联吡啶、4,4′-二(三甲基硅基)-2,2′-联吡啶、4,4′-二硝基-2,2′-联吡啶。其结构通过红外光谱、1H-NMR谱、元素分析等方法进行了表征。通过对这些配体在二氯甲烷溶液中的电子吸收和发射光谱的研究,结果表明不同取代基的吸/给电子能力差异显著影响配体的光学性质。取代基为三甲基硅基的配体呈现出最强的荧光强度,而取代基为硝基的配体则最弱。通过合成得到的4,4′-二取代-2,2′-联吡啶衍生物配体与cis-Ru(bpy)2·Cl2·2H2O反应,生成了一系列新型多吡啶钌(II)配合物。其结构通过红外、元素分析、1H-NMR和X-射线衍射等方法进行表征。以乙腈为溶剂,对这些配合物在溶液中的紫外吸收光谱进行了研究,结果表明配体上不同取代基对配合物的光学性质也产生了影响。钌(II)配合物的MLCT谱带在约450 nm,取代基为硝基的配合物吸收最强,而溴取代的配合物最弱。以450 nm为激发波长研究了配合物在乙腈溶液中的荧光性质,钌(II)配合物荧光发射最大波长均在610 nm左右,其中以取代基为三甲基硅基和甲氧基的配合物荧光强度最强,取代基为硝基的配合物荧光最弱。配合物的电化学行为的研究表明,四个配合物在乙腈溶液中都具有不可逆的氧化还原特性。本文还对得到的溴取代和甲氧基取代的2,2′-联吡啶钌(II)配合物的晶体结构进行了探讨。更多还原

【Abstract】 There are extensive interests in synthesis and properties of 2,2’-bipyridyl derivative with specifical function. Due to their coordinate ability to the metal, they have become one of most popular chelated ligands. Since ligand structure has important effect on electrochemical and photochemical properties of the complexes, many research works focused on substituting groups in aromatic ring. In this paper, a series of 4,4’-substitued-2,2’-bipyridyl and their Ru（II） complexes with electron-donating and electron-withdrawing substituents are synthesized and characterized with 2,2’-bipyridyl as raw material. The properties of ligands and their Ru（II） complexes are investigated in detail. Three crystal structures have been discussed.A series of 4,4’-substitued-2,2’-bipyridyl was synthesized by using 2,2’-bipyridyl as the starting material with a successive processes, such as N-oxidation, nitrification, halogenation, deoxygenation and silicification reaction. These ligands, 4,4’-dibromo-2,2’-bipyridyl, 4,4’- dimethoxy-2,2’-bipyridyl, 4,4’-bis（trimethylsilyl）-2,2’-bipyridyl and 4,4’-dinitro-2,2’-bipyridyl, are obtained. They are characterized with IR, 1H-NMR and element analysis. In the solution of methylene chloride, the result of UV-Vis absorption and emission reveals that electranical structure of ligang play an important role to their optical activities. The ligand with trimethylsilyl shows the strongest emission intensity, the poorest to that with nitro.The Ru（II） complexes have been alslo synthesized through the reaction between a series of 4,4’-substitued-2,2’-bipyridyl and cis-Ru（bpy）₂·Cl2·2H₂O. They are characterized with IR, element analysis, 1H-NMR, UV-Vis, emission spectra and X-ray diffraction. The UV-Vis spectra of Ru（II） complexes were collected in acetonitrile. The complexes with nitro and bromine atoms show the strongest and the poorest absorption respectively, while the MLCT bands at about 450 nm. Excitated at 450 nm, Ru（II） complexes sent emission at about 610 nm. The trimethylsilyl -substituented complex shows the strongest emission intensity, the weekest emission intensity for the nitro-substituented complex. The investigation of electrochemical behavior showed that these four Ru（II） complexes are irreversible in acetonitrile with LiCl·H₂O as the supporting electrolyte. We have also acheived single crystal materials of [Ru（bpy）₂（4,4′-dibromo-2,2′- bpy）]²⁺·2（PF6-） and [Ru（bpy）₂（4,4-dimethoxy-2,2′-bpy）]²⁺·2（PF6-）. Some information of structure is shown in detail.更多还原