金属铱配合物的合成及其应用研究

【作者】 李刘涛；

【导师】 杨红； 杨仕平；

【作者基本信息】 上海师范大学 ， 无机化学， 2011， 硕士

【摘要】 磷光铱配合物由于优良的光物理和光化学性质,如量子效率高、发射寿命长、发射波长易调节等,在磷光电致发光、生物成像、化学传感器等领域得到了广泛的应用。本文设计合成了三种不同的铱配合物,分别应用于细胞磷光标记、Cu²⁺化学传感器和磷光纳米材料,具体包括以下三个部分工作:1.基于PEG修饰的水溶性铱配合物的合成及其应用于细胞标记由于PEG具有良好的水溶性、脂溶性和生物相容性,广泛应用于生物化学领域的水溶性修饰基团。本工作通过Click反应将PEG引入到铱配合物中,得到水溶性铱配合物,并成功地应用于细胞的磷光标记。实验结果表明,该配合物细胞毒性很小,能选择性地对细胞胞浆区域进行染色。2.阳离子型铱配合物的合成及其应用于Cu²⁺化学传感器合成了一种含多个配位点的阳离子型铱配合物,实验发现,加入Cu²⁺前后,该铱配合物溶液的紫外-可见吸收光谱和磷光发射光谱都有发生明显变化,其对Cu²⁺的识别具有很高的选择性和优良的抗干扰性。对加入Cu²⁺前后的ESI-MS分析表明,该铱配合物可以与Cu²⁺发生特异性的配位作用,导致磷光发射的淬灭,从而实现Cu²⁺的有效检测,可以用做Cu²⁺的“turn-off”型磷光化学传感器。3.含吡啶铱配合物的合成及其在磷光纳米材料方面的应用探索设计合成了一种含有吡啶的铱磷光配合物,其与均苯三甲酸通过自组装的方法制备了微纳级立方体结构,并考察了不同的温度、投料比、搅拌时间、pH值对组装过程的影响,初步探索微纳级立方体的形成机理;其与均苯三甲酸三钠通过自组装的方法得到了形貌均匀的纳米线结构。更多还原

【Abstract】 Phosphorescent iridium complexes have attracted more and more attention due to their excellent photophysical and photochemical properties, such as high quantum efficiency, long life-time, easy to adjust the emission wavelength, etc.. They have been applied to biological imaging, chemical sensors, and optical function nanomaterials and so on. In this thesis, three types of iridium complexes were synthesized and were applied in phosphorescent cell marker, chemosensor for Cu²⁺ and nanomaterials. The details were shown as follows:1. PEG-modified water-soluble iridium complexes for cell markers Generally, PEG is a good water-soluble, biocompatible, fat-soluble, and widely applied in the fields of biochemistry. In this work, A water soluble iridium（III） complex was prepared by introducing PEG via click chemistry. The experiments showed that it had low cytotoxicity, good membrane permeability and exclusive staining in cytoplasm, which can be an excellent promising candidate for the design of new generation luminescent bioprobes.2. Cationic iridium complex and its application to chemosensor for Cu²⁺ The cationic iridium complex containing a number of coordination sites was synthesized. This complex has been shown to display extreme selectivity for Cu²⁺ over other metal ions. The signaling changes are observed through UV/Vis absorption, fluorescence emission. The ESI-MS analysis confirmed that the iridium complex was coordinated with Cu²⁺, leading to phosphorescence emission quenching. Therefore, it can be used as“turn-off”type phosphorescent chemical sensor for Cu²⁺.3. Iridium complex with pyridine groups to apply for phosphorescent nanomaterials A phosphorescent iridium complex containing pyridine groups was synthesized. The micro/nano cube structure were prepared by molecular self-assembly with benzene-1,3,5-tricarboxylic acid. The effect of different temperature, ratio, reaction time, pH value on the self-assembly process was investigated in details. The mechanism was discussed according to the crystal structure between the iridium complex and benzene-1,3,5-tricarboxylic acid. By the similar molecular self-assembly with benzene-1,3,5-tricarboxylic sodium salt, phosphorescent nanowires were also obtained.更多还原