本文選題：聚集誘導(dǎo)發(fā)光 + 熒光猝滅��； 參考：《江西師范大學》2017年碩士論文

【摘要】：在研究有機熒光分子光物理特性及其應(yīng)用領(lǐng)域時,大部分的有機熒光材料在稀溶液時熒光強度很高,而當分子濃度較高或者聚集態(tài)時,分子的發(fā)光強度和發(fā)光效率會急劇下降導(dǎo)致熒光猝滅(ACQ)現(xiàn)象。但在實際應(yīng)用中,有機活性材料普遍處于聚集態(tài),從而極大限制了其在不同領(lǐng)域的應(yīng)用。聚集誘導(dǎo)發(fā)光(AIE)是與ACQ完全相反的現(xiàn)象,即有機活性物質(zhì)在單分子形態(tài)或稀溶液時熒光很弱,在聚集程度較高時會發(fā)出強的熒光。它可以很好解決熒光材料在實際應(yīng)用的ACQ難題,因此在有機固體發(fā)光領(lǐng)域中具有很好的應(yīng)用前景。目前,已經(jīng)設(shè)計合成出了多種具有AIE特性的材料;其中,具有AIE效應(yīng)的四苯基乙烯(TPE)及其衍生物,因其發(fā)光性能出眾,合成方法簡便,應(yīng)用途徑廣泛而受到研究者的青睞。本文主要以TPE為核心單元,合成了一系列具有聚集誘導(dǎo)發(fā)光性能TPE聚合物和TPE小分子材料。第一部分:通過Suzuki交叉偶聯(lián)反應(yīng),將具有AIE特性的TPE單元引入到含銥配合物的聚合物主鏈中,得到一系列含TPE的磷光聚合物。通過改變聚合物中銥配合物的種類和含量,研究了磷光聚合物的熱力學性能和光物理性能。同時,通過研究磷光聚合物的聚集誘導(dǎo)發(fā)光性能發(fā)現(xiàn)聚合物兼有AIE和ACQ效應(yīng)。第二部分:以苯并噻二唑和苯并硒二唑為電子受體單元,以三苯胺和TPE作為電子給體單元合成了四種含推拉電子結(jié)構(gòu)(D-A)的化合物:TPE-BT-TPE、TPE-BTSe-TPE、TPA-BTSe-TPE和TPA-BTSe-TPE。研究了不同D-A結(jié)構(gòu)對化合物的熱力學性能和光物理性能的影響。由于存在分子內(nèi)的能量轉(zhuǎn)移和分子內(nèi)旋轉(zhuǎn)受限作用,化合物的熒光發(fā)光強度隨聚集狀態(tài)的增強呈現(xiàn)先減小后增大的發(fā)光特性。第三部分:以TPE為給體單元,二苯并噻吩為受體單元,合成了化合物TPE-DBT-TPE,研究了其光物理、電化學特性和聚集誘導(dǎo)發(fā)光特性。將TPE-DBT-TPE與聚甲基丙烯酸甲酯(PMMA)按一定比例溶解在干燥的DMF溶液中得到前驅(qū)體溶液,利用靜電紡絲技術(shù)制備了TPE-DBT-TPE/PMMA復(fù)合納米纖維,探究了纖維直徑和不同TPE-DBT-TPE濃度對復(fù)合納米纖維的發(fā)光強、熒光量子效率的影響。
[Abstract]:When studying the photophysical properties of organic fluorescence molecules and their application fields, the fluorescence intensity of most organic fluorescent materials is very high in dilute solution, but when the molecular concentration is high or the aggregation state is high, The luminescence intensity and luminescence efficiency of the molecule will decrease sharply, resulting in the fluorescence quenching of ACQ. However, in practical applications, organic active materials are generally in the aggregate state, which greatly limits their applications in different fields. Agglomeration induced luminescence (AIEs) is an opposite phenomenon to ACQ, that is, the fluorescence of organic active substances is very weak in monolayer or dilute solution, and strong fluorescence occurs when the aggregation degree is high. It can solve the ACQ problem of fluorescent materials in practical application, so it has a good application prospect in the field of organic solid state luminescence. At present, a variety of materials with AIE properties have been designed and synthesized. Among them, the tetraphenyl ethylene-tetraphenyl (AIE) and its derivatives have been favored by researchers for their outstanding luminescent properties, simple synthesis methods and wide applications. In this paper, a series of TPE polymers and TPE small molecular materials with aggregation induced luminescence properties were synthesized using TPE as the core unit. In the first part, a series of phosphorescent polymers containing TPE were obtained by introducing TPE units with AIE properties into the main chain of polymers containing iridium complexes by Suzuki cross-coupling reaction. The thermodynamic and photophysical properties of phosphorescent polymers were studied by changing the types and contents of iridium complexes in polymers. At the same time, the aggregation induced luminescence properties of phosphorescent polymers were studied. It was found that the polymers had both AIE and ACQ effects. In the second part, four compounds containing push-pull electronic structure (TPA-BT-TPEN), TPA-BTSe-TPE and TPA-BTSe-TPE were synthesized using benzothiadiazole and benzoselenediazole as electron receptor units and trianiline and TPE as electron donor units. The effects of different D-A structures on the thermodynamic and photophysical properties of the compounds were studied. Due to the existence of intramolecular energy transfer and intramolecular rotation confinement, the luminescence intensity of the compounds decreases first and then increases with the enhancement of the aggregation state. In the third part, the compound TPE-DBT-TPEwas synthesized with TPE as donor unit and dibenzothiophene as receptor unit. The photophysical, electrochemical and agglomeration induced luminescence properties of TPE-DBT-TPEwere studied. The precursor solution was obtained by dissolving TPE-DBT-TPE and polymethyl methacrylate (PMMA) in dry DMF solution in a certain proportion. TPE-DBT-TPE/PMMA composite nanofibers were prepared by electrostatic spinning technique. The effects of fiber diameter and TPE-DBT-TPE concentration on luminescence intensity and fluorescence quantum efficiency of composite nanofibers were investigated.
【學位授予單位】：江西師范大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O631.24;TQ340.1

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