具有聚集诱导发光性质的铱配合物的设计合成及其光电功能性质研究

发布时间：2018-03-12 14:17

本文选题：金属铱配合物　切入点：聚集诱导发光　出处：《东北师范大学》2016年硕士论文　论文类型：学位论文

【摘要】：如何快速高效地检测爆炸物对于国土安全和环境保护都具有十分重要的意义。目前,常用的爆炸物检测方法有以下几种：气相色谱,拉曼光谱,循环伏安,荧光传感等。其中荧光传感技术相对于其它方法具有更加简单、灵敏度更高、成本更低、响应时间更短等优点,备受人们的青睐。经过多年的努力,科研工作者已经成功的研制出基于高分子材料、有机金属骨架、纳米材料和有机染料的荧光探针。荧光材料在传感过程中其背景荧光信号可能会影响传感器的检测效果,与此相反,磷光材料具有相对较长的激发态寿命,可以有效地通过时间分辨技术消除荧光背景信号。此外,发展高效荧光传感器一个重大挑战就是如何克服因聚集而导致的发光淬灭(ACQ)现象。常规的发光材料分散在水合体系或聚合在固体状态时,多数会因为ACQ效应导致发光淬灭,大大降低了传感器的效率和灵敏度。为解决ACQ效应,人们尝试了各种化学方法和物理方法,但这些方法往往带来不同的负面影响。目前克服ACQ现象较为理想的办法是合成一种新型的聚集诱导发光(AIE)材料,这种聚集诱导发光现象是由唐本忠课题组于2001年首次发现的。相比于溶液状态,AIE材料在水环境或者聚集状态时呈现出较高的发光强度,有效地抑制了ACQ效应。AIE材料现已被广泛的应用于电致发光器件、化学传感和生物探针等方面。毫无疑问,AIE材料为设计合成适应于水环境的新型高效化学传感材料提供了一种新的思路。尽管现在对于爆炸物检测的技术已经相当成熟,但是由于硝基爆炸物的电子亲和性非常相近,如何能够选择性检测硝基爆炸物依然是一个具有挑战性的课题。在硝基爆炸物中,2,4,6-三硝基苯酚(TNP)在某种程度上破坏力强于2,4,6-三硝基甲苯(TNT),而且TNP被广泛应用于烟花、染料和火柴等日常用品中,非常容易污染土壤和水环境。因此,我们非常迫切的需要找到一种能够高效快速选择性检测TNP的方法。金属铱配合物因为其发光效率高、发光颜色可调、良好的光热稳定性、相对长的激发态寿命和大的Stokes位移等诸多优点,逐渐成为了研究热点。目前,人们已经成功的将具有AIE性质的磷光铱配合物应用于化学探针和细胞成像。在本论文中,我们结合聚集诱导发光特点和金属铱配合物本身的磷光特性,发展了一系列可用于高效、选择性检测TNP的磷光AIE材料,相关内容如下：(1)我们以苯基吡啶为环金属配体,吡啶基三氮唑衍生物为辅助配体设计合成了一种具有AIE性质的阳离子型金属铱配合物。发现其可以选择性地检测TNP,这是具有AIE性质的金属铱配合物在TNP选择性检测方面的首次应用。通过对比实验分析与理论计算,我们发现电子转移(PET)与共振能量转移共同导致了这种现象的发生。(2)我们合成了一系列基于二氟苯基吡唑为环金属配体的阳离子型金属铱配合物,其均表现出明显的AIE特性。通过改变配合物的发射波长,增强了配合物与TNP之间的能量转移,我们得到了检测TNP灵敏度更高的阳离子型AIE金属铱配合物。
[Abstract]:How to quickly and efficiently detect explosives is very important for Homeland Security and environmental protection. At present, there are several methods for detection of explosives used: gas chromatography, Raman spectroscopy, cyclic voltammetry, fluorescence sensing. The fluorescence sensing technology with respect to its IT method is more simple, higher sensitivity, lower cost shorter response time, etc., it is popular with people. After years of efforts, researchers have successfully developed based on polymer materials, metal organic frameworks, fluorescent nano materials and organic dyes. The fluorescent materials in the sensing process the background fluorescence signal may affect the detection effect of the sensor, on the contrary, phosphorescence the material has a relatively long lifetime of the excited state, can effectively eliminate the technology by time resolved fluorescence background signal. In addition, the development of high efficiency fluorescent sensor A major challenge is how to overcome aggregation caused by luminescence quenching (ACQ). The conventional light emitting material dispersed in the hydration system or polymerization in the solid state, because most ACQ effect leads to luminescence quenching, greatly reduces the efficiency and sensitivity of the sensor. In order to solve the ACQ effect, people have tried various the chemical and physical methods, but these methods often have a negative impact. The different ideal way to overcome the ACQ phenomenon is the synthesis of a new type of aggregation induced emission (AIE) materials, the aggregation induced emission phenomenon was first discovered by Tang Benzhong group in 2001. Compared to the solution, AIE materials in water environment or aggregation when showing a higher luminous intensity, and effectively suppress the ACQ effect of.AIE materials have been widely used in electroluminescent devices, chemical sensors and biological probes. There is no doubt that the AIE material provides a new idea for the design and synthesis of new efficient chemical sensing material adapted to the water environment. Although now for explosives detection technology has been quite mature, but due to the electron affinity of the nitro explosives are very similar to the selective detection of nitro explosives is still a challenge the subject. In the nitro explosives, 2,4,6- three nitro phenol (TNP) to a certain extent strong destructive force in 2,4,6- three (TNT), nitrotoluene and TNP are widely used in fireworks, dyes and matches of daily necessities, very easy to pollute the soil and water environment. Therefore, we urgently need find a way to efficient and selective detection of TNP. The metal iridium complexes because of its high luminous efficiency, light color adjustable, good thermal stability and lifetime of the excited state is relatively long and large Stok ES has many advantages such as displacement, gradually become a research hotspot. At present, people will have successfully with AIE properties of phosphorescent iridium complexes used in chemical probe and cell imaging. In this thesis, we combine the aggregation induced emission characteristics and the characteristics of the metal iridium phosphorescent material itself, the development of a series of high efficiency AIE, selective detection of TNP phosphorescent materials, the relevant contents are as follows: (1) we use phenyl pyridine as ring metal ligand, three pyridyl triazole derivatives as a cation with AIE properties of iridium complexes were synthesized. The design of auxiliary ligands can selectively detect TNP, this is the first application of iridium with the property of AIE complexes in TNP selective detection. Through the analysis of theory and experiment, we found that the electron transfer (PET) leads to the occurrence of this phenomenon and the resonance energy transfer (2. ) we synthesized a series of cationic fluorine two phenyl pyrazole ring based on metal ligand metal iridium complexes, the AIE showed obvious characteristics. With the emission wavelengths by changing the enhanced cooperation between the TNP and the energy transfer, we tested the cationic TNP sensitivity is higher the AIE metal iridium complexes.

【学位授予单位】：东北师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641.4

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