新型β-二酮类有机硼配合物的设计、合成及力致变色性能研究

发布时间：2018-07-18 07:38

【摘要】：力致荧光变色材料是一类新型的力刺激响应智能材料,在外界刺激下可发生荧光波长和荧光强度的可逆变化。近些年来,因其在信息存储、商标防伪和微应力传感等诸多领域具有潜在的应用而得到了越来越多的关注。有机硼配合物以其独特的光化学和光物理性质在刺激响应功能材料领域已成为一类重要的分子体系。结合聚集诱导发光(AIE)分子中的四苯乙烯(TPE)分子具有扭曲共轭的结构特征以及固态发光效率高的优点。本论文将TPE接入二氟化硼β-二酮配合物,以其为分子骨架通过化学修饰引入不同类型的取代基,合成得了一系列TPE衍生物,主要研究了这些TPE衍生物的AIE性能和力刺激响应变色性能。本论文的主要内容如下:第一章重点对激发态分子的光物理过程、聚集诱导发光性能、四苯乙烯类聚集诱导发光材料的应用、有机硼配合物的应用以及有机发光变色材料的发展情况进行了主要介绍。第二章基于卤素效应合成了一系列的含TPE基团的二氟化硼β-二酮衍生物,主要研究了它们的光物理性质、AIE性质、力致变色性质。结果表明,目标分子具有良好的AIE性能,力致变色性能明显,其变色机理是源自晶态到无定型态的可逆转变。另外,此类分子力致诱导发光红移的原因是由于在压力下发生分子构象平面化使其共轭程度增大,进而导致了固态吸收光谱的拓宽和荧光发射光谱的红移。此外,我们还发现TPEDKBF2Br具有荧光自恢复性能,其原因可能是该分子具有较强的结晶性能。第三章我们考察了烷基链对母体分子荧光性能的影响,详细研究了它们的AIE性能和力致变色性能。研究发现,五个化合物都具有良好的AIE性能;化合物TPEDKBF2OMe,TPEDKBF2OBu,和TPEDKBF2OHe的晶体具有张力(各向同性力)诱导发射波长蓝移和荧光增强性质,其原因是由于张力破坏了原来紧密堆积的晶体,使得晶体中的部分相互作用力得以释放,形成了排列较为疏松的微晶;另外,五个化合物在各向异性力的作用力下都表现出了发射波长红移的性质。此外,通过热力学性能研究还发现目标分子研磨后荧光恢复所需温度随着烷基链的增长逐渐降低,因此可通过烷基链的修饰来调控AIE分子对温度的响应性。最后我们通过对单晶的分析发现长的的烷基链会使得分子在单晶中排列时形成许多大的空腔,使得所培养的晶体比较容易在外力作用下发生无定型化。第四章合成了母体分子末端为二甲氨基、二苄氨基和咔唑基的三个化合物,主要研究了刚性含氮基团与柔性含氮基团对目标分子发光效率及力致发光变色的影响。研究结果表明化合物TPEDKBF2Ca具有良好的AIE性能,也表现出了力致发光红移的变色性能,但变色对比度不足。TPEDKBF2DMeA分子在溶液中的发光效率良好(在甲苯中达到了45.5%),但在晶体状态下的发光效率较低仅有18.8%,表现出了聚集诱导荧光猝灭(ACQ)的性质;其力致变色性能也较差,研磨前后仅有10nm的移动。TPEDKBF2DBeA展现了溶液和固态都能发光的二元发光(DSE)特性。在力致变色方面,展现了研磨诱导发光蓝移的现象,我们分析认为该化合物在晶相中分子排列紧密具有较大共轭程度,而研磨后的无定型态中分子构象较为扭曲,整体的共轭程度较小,因此研磨导致发光波长蓝移。另外,该化合物的结晶性较差,无法通过加热和溶剂熏蒸手段使其从无定形态转变为晶态,进而不具有可逆变色性质。
[Abstract]:The force induced fluorescent material is a new kind of intelligent material for the response to the response of force stimulation. The fluorescence wavelength and fluorescence intensity can be reversible. In recent years, more and more attention has been paid for its potential applications in many fields, such as information storage, trademark anti counterfeiting and micro stress sensing. The unique photochemical and photophysical properties have become an important class of molecular systems in the field of stimulating response functional materials. The four styrene (TPE) molecules in the aggregation induced luminescence (AIE) molecules have the advantages of distorted conjugated structure characteristics and high efficiency of solid-state luminescence. This paper introduces TPE into the complex of two boron fluoride - two - ketones. A series of TPE derivatives were synthesized by chemical modification of the molecular skeleton, and a series of TPE derivatives were synthesized. The main contents of this paper are as follows: the main contents of this paper are as follows: the first chapter focuses on the light physical process of the excited states, the aggregation induced luminescence properties, four styrene class. The application of aggregated induced luminescent materials, the application of organo boron complexes and the development of organic light-emitting materials were introduced. The second chapter, based on halogen effect, synthesized a series of two boron fluoride beta two ketones containing TPE groups, mainly studied their photophysical properties, AIE properties, and the properties of force Chromism. It is shown that the target molecules have good AIE properties, and the mechanism of discoloration is derived from the reversible transition from crystalline to amorphous. In addition, the cause of the red shift induced by this kind of molecular force is that the conjugated range of the molecule is increased by the conformation of molecular conformation under pressure, which leads to the widening of the solid absorption spectrum. In addition, we also found that TPEDKBF2Br has self recovery properties of fluorescence, which may be due to the strong crystalline properties of the molecule. In the third chapter, we investigated the effect of alkyl chains on the fluorescence properties of mother molecules, and studied their AIE properties and force photochromic properties in detail. The study found that five compounds were found. All of them have good AIE properties; compounds TPEDKBF2OMe, TPEDKBF2OBu, and TPEDKBF2OHe have tension (isotropic force) induced emission wavelength blue shift and fluorescence enhancement. The reason is that tension destroys the original tightly packed crystals, making the phase separation interaction in the crystal release, forming a relatively loose arrangement. In addition, the five compounds exhibit the characteristics of the red shift of the emission wavelengths under the force of anisotropic force. In addition, through the study of the thermodynamic properties, the temperature required for the recovery of the target molecules after the grinding of the target molecules gradually decreases with the increase of the alkyl chain, so the modification of the alkyl chain can be passed to regulate the response of the AIE molecules to the temperature. Finally, we find that a long alkyl chain can make a large number of large cavities formed when the molecules are arranged in a single crystal, so that the cultured crystals are easier to be amorphous under external force. In the fourth chapter, three compounds with the terminal of the mother molecule of two methylamino, two benzylamino and carbazole groups are synthesized. The effect of rigid nitrogen group and flexible nitrogen group on the luminescence and luminescence of the target molecules is studied. The results show that the compound TPEDKBF2Ca has good AIE properties, and also shows the color change performance of the red shift of the force luminescence, but the luminescence efficiency of the.TPEDKBF2DMeA molecule in the solution is good. It has reached 45.5% in toluene, but it has a low luminescence efficiency of only 18.8% in the crystal state, showing the properties of aggregation induced fluorescence quenching (ACQ), and its discoloration performance is poor. The mobile.TPEDKBF2DBeA with only 10nm before and after grinding shows the two element luminescence (DSE) properties of both solution and solid state. The phenomenon of blue shift induced by lapping is found. It is concluded that the molecular arrangement of the compound in the crystal phase is highly conjugated, and the molecular conformation in the amorphous state after grinding is distorted and the overall conjugation degree is small, so the lapping leads to the blue shift of the luminescence wavelength. And solvent fumigation means that it changes from amorphous to crystalline, and has no reversible color change.
【学位授予单位】：石河子大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4;TB381

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