本文選題：金屬銥配合物　切入點：聚集誘導發(fā)光　出處：《東北師范大學》2016年碩士論文　論文類型：學位論文

【摘要】：如何快速高效地檢測爆炸物對于國土安全和環(huán)境保護都具有十分重要的意義。目前,常用的爆炸物檢測方法有以下幾種：氣相色譜,拉曼光譜,循環(huán)伏安,熒光傳感等。其中熒光傳感技術(shù)相對于其它方法具有更加簡單、靈敏度更高、成本更低、響應(yīng)時間更短等優(yōu)點,備受人們的青睞。經(jīng)過多年的努力,科研工作者已經(jīng)成功的研制出基于高分子材料、有機金屬骨架、納米材料和有機染料的熒光探針。熒光材料在傳感過程中其背景熒光信號可能會影響傳感器的檢測效果,與此相反,磷光材料具有相對較長的激發(fā)態(tài)壽命,可以有效地通過時間分辨技術(shù)消除熒光背景信號。此外,發(fā)展高效熒光傳感器一個重大挑戰(zhàn)就是如何克服因聚集而導致的發(fā)光淬滅(ACQ)現(xiàn)象。常規(guī)的發(fā)光材料分散在水合體系或聚合在固體狀態(tài)時,多數(shù)會因為ACQ效應(yīng)導致發(fā)光淬滅,大大降低了傳感器的效率和靈敏度。為解決ACQ效應(yīng),人們嘗試了各種化學方法和物理方法,但這些方法往往帶來不同的負面影響。目前克服ACQ現(xiàn)象較為理想的辦法是合成一種新型的聚集誘導發(fā)光(AIE)材料,這種聚集誘導發(fā)光現(xiàn)象是由唐本忠課題組于2001年首次發(fā)現(xiàn)的。相比于溶液狀態(tài),AIE材料在水環(huán)境或者聚集狀態(tài)時呈現(xiàn)出較高的發(fā)光強度,有效地抑制了ACQ效應(yīng)。AIE材料現(xiàn)已被廣泛的應(yīng)用于電致發(fā)光器件、化學傳感和生物探針等方面。毫無疑問,AIE材料為設(shè)計合成適應(yīng)于水環(huán)境的新型高效化學傳感材料提供了一種新的思路。盡管現(xiàn)在對于爆炸物檢測的技術(shù)已經(jīng)相當成熟,但是由于硝基爆炸物的電子親和性非常相近,如何能夠選擇性檢測硝基爆炸物依然是一個具有挑戰(zhàn)性的課題。在硝基爆炸物中,2,4,6-三硝基苯酚(TNP)在某種程度上破壞力強于2,4,6-三硝基甲苯(TNT),而且TNP被廣泛應(yīng)用于煙花、染料和火柴等日常用品中,非常容易污染土壤和水環(huán)境。因此,我們非常迫切的需要找到一種能夠高效快速選擇性檢測TNP的方法。金屬銥配合物因為其發(fā)光效率高、發(fā)光顏色可調(diào)、良好的光熱穩(wěn)定性、相對長的激發(fā)態(tài)壽命和大的Stokes位移等諸多優(yōu)點,逐漸成為了研究熱點。目前,人們已經(jīng)成功的將具有AIE性質(zhì)的磷光銥配合物應(yīng)用于化學探針和細胞成像。在本論文中,我們結(jié)合聚集誘導發(fā)光特點和金屬銥配合物本身的磷光特性,發(fā)展了一系列可用于高效、選擇性檢測TNP的磷光AIE材料,相關(guān)內(nèi)容如下：(1)我們以苯基吡啶為環(huán)金屬配體,吡啶基三氮唑衍生物為輔助配體設(shè)計合成了一種具有AIE性質(zhì)的陽離子型金屬銥配合物。發(fā)現(xiàn)其可以選擇性地檢測TNP,這是具有AIE性質(zhì)的金屬銥配合物在TNP選擇性檢測方面的首次應(yīng)用。通過對比實驗分析與理論計算,我們發(fā)現(xiàn)電子轉(zhuǎn)移(PET)與共振能量轉(zhuǎn)移共同導致了這種現(xiàn)象的發(fā)生。(2)我們合成了一系列基于二氟苯基吡唑為環(huán)金屬配體的陽離子型金屬銥配合物,其均表現(xiàn)出明顯的AIE特性。通過改變配合物的發(fā)射波長,增強了配合物與TNP之間的能量轉(zhuǎn)移,我們得到了檢測TNP靈敏度更高的陽離子型AIE金屬銥配合物。
[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.

【學位授予單位】：東北師范大學
【學位級別】：碩士
【學位授予年份】：2016
【分類號】：O641.4

【參考文獻】

相關(guān)博士學位論文 前1條

1 單國剛;新型陽離子銥金屬配合物的設(shè)計合成及其性質(zhì)的研究[D];東北師范大學;2012年

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本文編號：1601923