衍生化氰基二苯乙烯及萘二酰亚胺类功能分子的超分子组装新体系

发布时间：2018-07-01 19:58

  本文选题：自组装 + 形貌　； 参考：《山东大学》2017年硕士论文

【摘要】：近年来,超分子化学已发展成为与物理学科,材料学科,生物学科等紧密相连的一类交叉学科。本论文以具有光响应性的二苯乙烯衍生物和具有良好电荷效应的萘二酰亚胺衍生物为研究对象,研究了其组装特征、光致异构特点、电荷转移效应等,还探索了其潜在应用。论文主要包括三部分:第一章,对超分子组装、组装结构及影响因素,二苯乙烯衍生物的组装及应用,萘二酰亚胺衍生物的组装及应用做了简单的介绍。第二章,主要研究了羟基修饰的氰基二苯乙烯分子在良/不良溶剂中的组装。我们发现通过调节溶剂的极性,组装体系的微观形貌可以实现由囊泡到纤维再到球状聚集体的转变。囊泡的尺寸在240nm左右,而纤维的尺寸可以达到微米级别。组装体的微观形貌通过透射电镜、扫描电镜、原子力显微镜等手段得到验证。因为氰基二苯乙烯衍生物是一类具有荧光性质的分子,我们对组装体系进行紫外光谱和荧光光谱测定。发现随着混合溶剂中不良溶剂的增多,紫外吸收发生明显的降低,荧光发射强度在460nm处的出现增强的趋势,这说明体系中发生了组装行为。组装形态在电镜下可以清楚的观察到。因为二苯乙烯衍生物还是一类具有光致异构化性质的分子。在光刺激下可以发生Z-构型向E-构型的转变,分子构型的转变导致组装结构发生变化。透射电镜下可以观察到不同光刺激下,体系中的微观形貌的变化趋势。囊泡结构逐渐解离成无序状,棒状结构则变成片状结构。构型转变后,体系的荧光因分子内扭转电荷转移效应受到限制而增强。核磁和质谱数据表明在紫外光作用下,分子只发生了构型变化,没有任何新反应发生,也就是说是构型的变化导致了组装形貌及性质的变化。我们还将染料分子罗丹明引入体系中,通过固定光照时间发现,混合体系在紫外光照射下可以得到不同色度的光。该想法为不同光材料的制备提供了可能性。第三章,主要研究了 N,N'-二丁酸基-1,4,5,8-萘二酰亚胺衍生物的在不同溶剂环境下的组装以及与富电子1-芘丁酸的电荷转移组装。我们发现在不同的溶剂下组装形貌是不同的。在水溶剂中,随着浓度的变化,1-芘丁酸的组装形貌由带状结构变化到片状结构。与萘二酰亚胺衍生物的复合体系(1:1摩尔比),随着浓度的变化,组装形貌则是尺寸较大的树枝状结构。紫外光谱图显示随着复合体系浓度增加,吸收强度逐渐增强,并且在400-600nm处有新峰产生,即电荷转移峰。而荧光发射强度则展现出逐渐降低的趋势。而在DMF溶剂中,1-芘丁酸组装成规则的球状聚集体,尺寸大约为70nm。与萘二酰亚胺衍生物的复合体系(1:1摩尔比),则组装成纤维结构,且随着浓度的变化,组装体系中出现环状结构。而在DMF/H2O混合溶剂中,N,N'-二丁酸基-1,4,5,8-萘二酰亚胺组装成锯齿状片状结构,长度可达l0μm,1-芘丁酸则组装成片状聚集体,随着浓度的增大,片状结构逐渐聚集成更大尺寸的花瓣状聚集体。二者的复合体系颜色变成紫红色,组装成了层层堆叠的状态,通过扫描电子显微镜可以清楚的观察到组装形貌。由紫外吸收光谱图的变化趋势我们选择DMF/H2O混合溶剂的的比例为1-9的体系为组装研究对象。在DMSO-H20混合溶剂中,N,N'-二丁酸基-1,4,5,8-萘二酰亚胺衍生物的组装成短棒,1-芘丁酸体系在SEM下可以观察到平铺在视野里的片状结构,复合体系则发现束状聚集体。通过变化溶剂,我们发现各组分的组装行为发生着变化,可以得到不同尺寸不同维度的微观形貌。说明控制溶剂极性可以得到不同的分子组装形貌。在研究中,由于N,N'-二丁酸基-1,4,5,8-萘二酰亚胺与1-芘丁酸的电荷密度不同,结构匹配性比较高,二者可以发生电荷转移,形成电荷转移复合体。而基于电荷转移效应的超分子自组装体系在电子器件,光材料等领域有着重要地位。
[Abstract]:In recent years, supramolecular chemistry has developed into a kind of interdisciplinary subject closely connected with physics, materials and biology. In this paper, two styrene derivatives with photoresponse and naphthalene imide derivatives with good charge effect have been studied, and their assembly characteristics, photoisomeric characteristics and charge transfer are studied. The potential applications are also explored. The thesis mainly includes three parts: Chapter 1, the assembly of supramolecular assembly, assembly structure and influencing factors, the assembly and application of two styrene derivatives, the assembly and application of naphthalene two imide derivatives are briefly introduced. Chapter second, the main purpose is to study the hydroxyl modified cyanyl two styrene molecules in good / good. We found that by adjusting the polarity of the solvent, the micromorphology of the assembly system can be transformed from vesicles to fibers to spherical aggregates. The size of the vesicles is about 240nm, and the size of the fibers can reach the micron level. The microstructure of the assembly body is transmitted by transmission electron microscopy, scanning electron microscopy, and atomic force microscopy. The cyanic two styrene derivatives are a class of molecules with fluorescence properties. The UV and fluorescence spectra of the system are determined by UV and fluorescence spectra. It is found that with the increase of bad solvent in the mixed solvent, the UV absorption is obviously reduced and the fluorescence intensity is increasing at 460nm. The assembly behavior occurred in the Ming system. The assembly morphology can be clearly observed under the electron microscope. Because the two styrene derivatives are still a class of molecules with photoisomerization properties. The transformation of the Z- configuration to the E- configuration can occur under the light stimulation. The transformation of the molecular configuration leads to the change of the assembly structure. Under transmission electron microscope, it can be observed by transmission electron microscope. The micromorphology changes in the system under different light stimuli. The vesicle structure is gradually disordered and the rod like structure turns into a flake structure. After the configuration changes, the fluorescence of the system is restricted by the intramolecular charge transfer effect. The NMR and MS data show that the molecule only has the configuration changes under the ultraviolet light. There is no new reaction, that is, the change in the configuration leads to changes in the morphology and properties of the assembly. We also introduce the dye molecule Luo Danming into the system to find that the mixed system can get different chromaticity light under UV light. This method provides the possibility for the preparation of different optical materials. In the third chapter, we mainly studied the assembly of N, N'- two butyric -1,4,5,8- naphthalene two imide derivatives in different solvent environments and the charge transfer assembly with the rich electron 1- pyrene butyric acid. We found that the assembly morphology was different under different solvents. In water solvent, the assembly morphology of 1- pyrene was zonal with the change of concentration. The composite system (1:1 molar ratio) with naphthalene two imide derivatives (mole ratio), with the change of the concentration, the assembly morphology is a larger dendrimer structure. The UV spectra show that the absorption strength is gradually increased with the increase of the concentration of the composite system, and the peak of the charge transfer is produced at the 400-600nm. In DMF solvent, 1- pyrene is assembled into a regular spherical aggregate in a composite system of about 70nm. and naphthalene two imide derivatives (1:1 mole ratio), which is assembled into a fiber structure, and as the concentration changes, the ring structure appears in the assembly system. In the DMF/H2O mixed solvent, N, N'- two butyric -1,4,5,8- naphthalene two imide is assembled into a zigzag structure with a length of l0 mu m, and 1- pyrene butyric acid is assembled into patch aggregates. As the concentration increases, the flake structure gradually integrates into the larger size petal aggregates. The color of the two system becomes purple red and is assembled into layers of stacked state, through scanning. The electron microscope can clearly observe the assembly morphology. From the variation trend of the UV absorption spectrum, we choose the system of 1-9 of the DMF/H2O mixed solvent. In the DMSO-H20 mixed solvent, N, N'- two butyric -1,4,5,8- naphthalene two imide derivatives are assembled into short rods, and 1- pyrene butyric acid system can be used under SEM By changing the solvent, we found that the assembly behavior of each component was changed, and the micromorphology of different dimensions and dimensions could be obtained. It shows that the polarity of the solvent can be controlled by different molecular assembly morphology. In the study, N, N'- two D The charge density of acid based -1,4,5,8- naphthalene two imide and 1- pyrene is different, the structure matching is higher, the two can take charge transfer and form charge transfer complex, and the supermolecule self-assembly system based on charge transfer effect has a great importance in the fields of electronic devices, optical materials and so on.
【学位授予单位】：山东大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.3
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本文编号：2088986