中文题名: | 烷基链长度不同的双核多联吡啶钌配合物的研究 |
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保密级别: | 公开 |
学科代码: | 070301 |
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学生类型: | 硕士 |
学位: | 理学硕士 |
学位年度: | 2007 |
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研究方向: | 光电功能分子材料 |
第一导师姓名: | |
第一导师单位: | |
提交日期: | 2007-06-12 |
答辩日期: | 2007-06-10 |
中文关键词: | |
中文摘要: |
多联吡啶钌配合物以其卓越的光化学和光物理而吸引着越来越多的科学家投身到它的研究中去。充分利用多联吡啶钌配合物的这些性质,实现钌配合物的多功能和多用途是目前研究的热点。本论文工作包括下列三方面内容:(1). 本论文合成了六个配体和六个多联吡啶钌配合物。六个配体是:1,3-二-(2-(咪唑[4,5-f]1,10-邻菲啰啉)咔唑基)丙烷(L1)、1,10-二-(2-(咪唑[4,5-f]1,10-邻菲啰啉)咔唑基)癸烷(L3)、1-咔唑基-3-(2-(咪唑[4,5-f]1,10-邻菲啰啉)咔唑基)丙烷(L4)、1-咔唑基-6-(2-(咪唑[4,5-f]1,10-邻菲啰啉)咔唑基)己烷(L5)、1-咔唑基-10-(2-(咪唑[4,5-f]1,10-邻菲啰啉)咔唑基)癸烷(L6)和10,12-二甲基蝶啶[6,7-f][1,10]邻菲啰啉-11,13(10H,12H)-二酮(L7);六个配合物是:[Ru2L1(bpy)4]4+、[Ru2L3(bpy)4]4+、[Ru(bpy)2L4]2+、[Ru(bpy)2L5]2+、[Ru(bpy)2L6]2+和[Ru(bpy)2L7]2+。通过元素分析、氢核磁共振谱、红外光谱和基质辅助激光解析电离飞行时间质谱对合成的化合物进行了表征。(2). 通过紫外-可见吸收光谱和荧光光谱的pH滴定研究了[Ru2L1(bpy)4]4+、[Ru2L2(bpy)4]4+、[Ru2L3(bpy)4]4+和[Ru(bpy)2L7]2+ (bpy = 2,2-联吡啶)的酸碱性质,求算了这几个配合物的基态质子解离常数及激发态质子解离常数。结果表明,[Ru2L1(bpy)4]4+、[Ru2L2(bpy)4]4+和[Ru2L3(bpy)4]4+的紫外-可见光谱和荧光光谱均随溶液酸度的改变发生很大变化,而且这三个配合物可以作为质子诱导荧光开关,“on-off”比分别为30、61和55。[Ru(bpy)2L7]2+是一个不多见的良好的“off-on”荧光开关材料,“off-on”比值接近127。(3). 本文还通过紫外-可见光谱和荧光光谱滴定、稳态荧光淬灭、与DNA插入键合试剂溴化乙锭的DNA竞争健合、DNA热变性实验和粘度实验系统研究了[Ru2L1(bpy)4]4+、[Ru2L2(bpy)4]4+、[Ru2L3(bpy)4]4+和[Ru(bpy)2L7]2+的DNA健合性质。证明[Ru(bpy)2L7]2+以插入模式与DNA键合。而[Ru2L1(bpy)4]4+、[Ru2L2(bpy)4]4+和[Ru2L3(bpy)4]4+因为发生了二聚,与DNA作用行为比较特殊,推测可能是以插入方式与DNA键合的,有待继续深入的研究。
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外文摘要: |
Ruthenium polypyridine complexes have attracted much attention due to their superior photochemical and photophysical properties in recent years. The realization of multifunctionality of the ruthenium complexes is the main purpose of many researchers. This dissertation deals with the following: (1). Six ligands of (1,3-bis(([1,10]-phenanthroline[4,5-f]imidazol-2-yl)carbazoyl)propane (L1), 1,10-bis(([1,10]-phenanthroline[4,5-f]imidazol-2-yl)carbazoyl)decane (L3), 1-carbazoyl-3-(([1,10]-phenanthroline[4,5-f]imidazol-2-yl)carbazoyl)propane (L4), 1-carbazoyl-6-(([1,10]-phenanthroline[4,5-f]imidazol-2-yl)carbazoyl)hexane (L5), 1-carbazoyl-10-(([1,10]-phenanthroline[4,5-f]imidazol-2-yl)carbazoyl)decane (L6) and 10,12-dimethyl-pteridino[6,7-f][1,10]phenanthroline-11,13(10H,12H)-dione (L7)) and six complexes of ([Ru2L1(bpy)4]4+, [Ru2L3(bpy)4]4+, [Ru(bpy)2L4]2+, [Ru(bpy)2L5]2+, [Ru(bpy)2L6]2+ and [Ru(bpy)2L7]2+) have been synthesized and characterized by elemental analysis, 1H NMR, FT-IR spectroscopy, and MALDI-TOF Mass spectrometry.(2). The acid-base properties of [Ru2L1(bpy)4]4+, [Ru2L2(bpy)4]4+, [Ru2L3(bpy)4]4+ and [Ru(bpy)2L7]2+ have been studied by spectrophotometric pH titrations. It was found that the UV–visible absorption and emission spectra of [Ru2L1(bpy)4]4+, [Ru2L2(bpy)4]4+ and [Ru2L3(bpy)4]4+ were dramatically influenced by the solution acidities. The ground- and excited-state ionization constants of these three complexes have been derived. The three complexes act as “on-off” emission switchs with maximum on-off ratios of 30, 61 and 55, respectively. [Ru(bpy)2L7]2+ acted as a remarkable pH-induced “off-on” emission switch with a maximum off-on ratio of ~127. (3). The calf thymus DNA-binding properties of [Ru2L1(bpy)4]4+, [Ru2L2(bpy)4]4+, [Ru2L3(bpy)4]4+ and [Ru(bpy)2L7]2+ have been studied with UV/Vis absorption and luminescence titrations, steady-state emission quenching by [Fe(CN)6]4–, DNA competitive binding with ethidium bromide, and thermal denaturation of the DNA. The results show that [Ru(bpy)2L7]2+ bind to the DNA in an intercalative mode. While influenced by self association, the DNA-binding modes for [Ru2L1(bpy)4]4+, [Ru2L2(bpy)4]4+ and [Ru2L3(bpy)4]4+ are complicated, probably being in a intercalative mode, requiring further studies.
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参考文献总数: | 170 |
作者简介: | 以第一作者身份发表了两篇SCI收录的文章,以第二作者身份发表了一篇SCI收录的文章和一篇SCIE收录的文章。 |
馆藏号: | 硕070301/0706 |
开放日期: | 2007-06-12 |