四苯乙烯基聚集态诱导发光材料的合成及电纺发光纳米纤维的制备与性能研究

发布时间：2018-05-22 07:31

本文选题：聚集诱导发光 + 荧光猝灭　；参考：《江西师范大学》2017年硕士论文

【摘要】：在研究有机荧光分子光物理特性及其应用领域时,大部分的有机荧光材料在稀溶液时荧光强度很高,而当分子浓度较高或者聚集态时,分子的发光强度和发光效率会急剧下降导致荧光猝灭(ACQ)现象。但在实际应用中,有机活性材料普遍处于聚集态,从而极大限制了其在不同领域的应用。聚集诱导发光(AIE)是与ACQ完全相反的现象,即有机活性物质在单分子形态或稀溶液时荧光很弱,在聚集程度较高时会发出强的荧光。它可以很好解决荧光材料在实际应用的ACQ难题,因此在有机固体发光领域中具有很好的应用前景。目前,已经设计合成出了多种具有AIE特性的材料;其中,具有AIE效应的四苯基乙烯(TPE)及其衍生物,因其发光性能出众,合成方法简便,应用途径广泛而受到研究者的青睐。本文主要以TPE为核心单元,合成了一系列具有聚集诱导发光性能TPE聚合物和TPE小分子材料。第一部分:通过Suzuki交叉偶联反应,将具有AIE特性的TPE单元引入到含铱配合物的聚合物主链中,得到一系列含TPE的磷光聚合物。通过改变聚合物中铱配合物的种类和含量,研究了磷光聚合物的热力学性能和光物理性能。同时,通过研究磷光聚合物的聚集诱导发光性能发现聚合物兼有AIE和ACQ效应。第二部分:以苯并噻二唑和苯并硒二唑为电子受体单元,以三苯胺和TPE作为电子给体单元合成了四种含推拉电子结构(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结构对化合物的热力学性能和光物理性能的影响。由于存在分子内的能量转移和分子内旋转受限作用,化合物的荧光发光强度随聚集状态的增强呈现先减小后增大的发光特性。第三部分:以TPE为给体单元,二苯并噻吩为受体单元,合成了化合物TPE-DBT-TPE,研究了其光物理、电化学特性和聚集诱导发光特性。将TPE-DBT-TPE与聚甲基丙烯酸甲酯(PMMA)按一定比例溶解在干燥的DMF溶液中得到前驱体溶液,利用静电纺丝技术制备了TPE-DBT-TPE/PMMA复合纳米纤维,探究了纤维直径和不同TPE-DBT-TPE浓度对复合纳米纤维的发光强、荧光量子效率的影响。
[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.
【学位授予单位】：江西师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631.24;TQ340.1

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