本文選題：自組裝 + 形貌�。� 參考：《山東大學(xué)》2017年碩士論文

【摘要】：近年來(lái),超分子化學(xué)已發(fā)展成為與物理學(xué)科,材料學(xué)科,生物學(xué)科等緊密相連的一類交叉學(xué)科。本論文以具有光響應(yīng)性的二苯乙烯衍生物和具有良好電荷效應(yīng)的萘二酰亞胺衍生物為研究對(duì)象,研究了其組裝特征、光致異構(gòu)特點(diǎn)、電荷轉(zhuǎn)移效應(yīng)等,還探索了其潛在應(yīng)用。論文主要包括三部分:第一章,對(duì)超分子組裝、組裝結(jié)構(gòu)及影響因素,二苯乙烯衍生物的組裝及應(yīng)用,萘二酰亞胺衍生物的組裝及應(yīng)用做了簡(jiǎn)單的介紹。第二章,主要研究了羥基修飾的氰基二苯乙烯分子在良/不良溶劑中的組裝。我們發(fā)現(xiàn)通過(guò)調(diào)節(jié)溶劑的極性,組裝體系的微觀形貌可以實(shí)現(xiàn)由囊泡到纖維再到球狀聚集體的轉(zhuǎn)變。囊泡的尺寸在240nm左右,而纖維的尺寸可以達(dá)到微米級(jí)別。組裝體的微觀形貌通過(guò)透射電鏡、掃描電鏡、原子力顯微鏡等手段得到驗(yàn)證。因?yàn)榍杌揭蚁┭苌锸且活惥哂袩晒庑再|(zhì)的分子,我們對(duì)組裝體系進(jìn)行紫外光譜和熒光光譜測(cè)定。發(fā)現(xiàn)隨著混合溶劑中不良溶劑的增多,紫外吸收發(fā)生明顯的降低,熒光發(fā)射強(qiáng)度在460nm處的出現(xiàn)增強(qiáng)的趨勢(shì),這說(shuō)明體系中發(fā)生了組裝行為。組裝形態(tài)在電鏡下可以清楚的觀察到。因?yàn)槎揭蚁┭苌镞�是一類具有光致異構(gòu)化性質(zhì)的分子。在光刺激下可以發(fā)生Z-構(gòu)型向E-構(gòu)型的轉(zhuǎn)變,分子構(gòu)型的轉(zhuǎn)變導(dǎo)致組裝結(jié)構(gòu)發(fā)生變化。透射電鏡下可以觀察到不同光刺激下,體系中的微觀形貌的變化趨勢(shì)。囊泡結(jié)構(gòu)逐漸解離成無(wú)序狀,棒狀結(jié)構(gòu)則變成片狀結(jié)構(gòu)。構(gòu)型轉(zhuǎn)變后,體系的熒光因分子內(nèi)扭轉(zhuǎn)電荷轉(zhuǎn)移效應(yīng)受到限制而增強(qiáng)。核磁和質(zhì)譜數(shù)據(jù)表明在紫外光作用下,分子只發(fā)生了構(gòu)型變化,沒有任何新反應(yīng)發(fā)生,也就是說(shuō)是構(gòu)型的變化導(dǎo)致了組裝形貌及性質(zhì)的變化。我們還將染料分子羅丹明引入體系中,通過(guò)固定光照時(shí)間發(fā)現(xiàn),混合體系在紫外光照射下可以得到不同色度的光。該想法為不同光材料的制備提供了可能性。第三章,主要研究了 N,N'-二丁酸基-1,4,5,8-萘二酰亞胺衍生物的在不同溶劑環(huán)境下的組裝以及與富電子1-芘丁酸的電荷轉(zhuǎn)移組裝。我們發(fā)現(xiàn)在不同的溶劑下組裝形貌是不同的。在水溶劑中,隨著濃度的變化,1-芘丁酸的組裝形貌由帶狀結(jié)構(gòu)變化到片狀結(jié)構(gòu)。與萘二酰亞胺衍生物的復(fù)合體系(1:1摩爾比),隨著濃度的變化,組裝形貌則是尺寸較大的樹枝狀結(jié)構(gòu)。紫外光譜圖顯示隨著復(fù)合體系濃度增加,吸收強(qiáng)度逐漸增強(qiáng),并且在400-600nm處有新峰產(chǎn)生,即電荷轉(zhuǎn)移峰。而熒光發(fā)射強(qiáng)度則展現(xiàn)出逐漸降低的趨勢(shì)。而在DMF溶劑中,1-芘丁酸組裝成規(guī)則的球狀聚集體,尺寸大約為70nm。與萘二酰亞胺衍生物的復(fù)合體系(1:1摩爾比),則組裝成纖維結(jié)構(gòu),且隨著濃度的變化,組裝體系中出現(xiàn)環(huán)狀結(jié)構(gòu)。而在DMF/H2O混合溶劑中,N,N'-二丁酸基-1,4,5,8-萘二酰亞胺組裝成鋸齒狀片狀結(jié)構(gòu),長(zhǎng)度可達(dá)l0μm,1-芘丁酸則組裝成片狀聚集體,隨著濃度的增大,片狀結(jié)構(gòu)逐漸聚集成更大尺寸的花瓣?duì)罹奂w。二者的復(fù)合體系顏色變成紫紅色,組裝成了層層堆疊的狀態(tài),通過(guò)掃描電子顯微鏡可以清楚的觀察到組裝形貌。由紫外吸收光譜圖的變化趨勢(shì)我們選擇DMF/H2O混合溶劑的的比例為1-9的體系為組裝研究對(duì)象。在DMSO-H20混合溶劑中,N,N'-二丁酸基-1,4,5,8-萘二酰亞胺衍生物的組裝成短棒,1-芘丁酸體系在SEM下可以觀察到平鋪在視野里的片狀結(jié)構(gòu),復(fù)合體系則發(fā)現(xiàn)束狀聚集體。通過(guò)變化溶劑,我們發(fā)現(xiàn)各組分的組裝行為發(fā)生著變化,可以得到不同尺寸不同維度的微觀形貌。說(shuō)明控制溶劑極性可以得到不同的分子組裝形貌。在研究中,由于N,N'-二丁酸基-1,4,5,8-萘二酰亞胺與1-芘丁酸的電荷密度不同,結(jié)構(gòu)匹配性比較高,二者可以發(fā)生電荷轉(zhuǎn)移,形成電荷轉(zhuǎn)移復(fù)合體。而基于電荷轉(zhuǎn)移效應(yīng)的超分子自組裝體系在電子器件,光材料等領(lǐng)域有著重要地位。
[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.
【學(xué)位授予單位】：山東大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.3
，

本文編號(hào)：2088986