本文選題：TPE + AIE　； 參考：《中國(guó)礦業(yè)大學(xué)》2017年碩士論文

【摘要】：聚集誘導(dǎo)發(fā)光(AIE)物質(zhì)在固態(tài)或者聚集狀態(tài)下,因?yàn)榕で鷺?gòu)象、堆積形態(tài)等變化導(dǎo)致其熒光發(fā)射的波長(zhǎng)和強(qiáng)度發(fā)生改變,使其在有機(jī)發(fā)光二極管(OLED)、熒光生物探針等領(lǐng)域具有廣闊的應(yīng)用前景。作為典型聚集誘導(dǎo)發(fā)光物質(zhì)的四苯乙烯(TPE),近些年來(lái)引起了人們廣泛的關(guān)注。本論文以希夫堿為結(jié)構(gòu)中心,利用四苯乙烯與一系列水楊醛衍生物反應(yīng),設(shè)計(jì)合成八種希夫堿,并對(duì)它們的光物理光化學(xué)性質(zhì)進(jìn)行了較為系統(tǒng)的研究。初步探索了相關(guān)化合物的結(jié)晶誘導(dǎo)發(fā)光增強(qiáng)CEE(crystallization enhanced emission),分子內(nèi)扭曲電荷轉(zhuǎn)移(TICT),壓致變色(piezallochromy),激發(fā)態(tài)分子內(nèi)質(zhì)子轉(zhuǎn)移(ESIPT)等機(jī)理和應(yīng)用。具體研究結(jié)果如下:1.以四苯乙烯為底物合成四苯乙烯胺(TPE-NH2),以水楊醛為底物合成一系列水楊醛衍生物。四苯乙烯胺分別與水楊醛、5-溴水楊醛、5-氯水楊醛、5-氰基水楊醛通過(guò)醛胺縮合反應(yīng)合成四種希夫堿分子,分別對(duì)應(yīng)為化合物1至化合物4。通過(guò)研究目標(biāo)產(chǎn)物的光學(xué)性質(zhì)發(fā)現(xiàn),在四氫呋喃(THF)中加入不良溶劑水時(shí),隨著水組分的增加,混合溶液的熒光逐漸增強(qiáng),也就是說(shuō)四種希夫堿均具有聚集誘導(dǎo)發(fā)光增強(qiáng)性質(zhì)。當(dāng)含水的混合溶液靜置一段時(shí)間后,發(fā)現(xiàn)化合物2,3和4的混合溶液熒光強(qiáng)度相比與靜置前,發(fā)生了明顯的增強(qiáng),且最大發(fā)射波長(zhǎng)也發(fā)生了藍(lán)移。該系列化合物的聚集態(tài)發(fā)光現(xiàn)象可歸因于聚集體的結(jié)晶化。這種變化的時(shí)間依賴性與分子結(jié)晶速度和結(jié)晶化程度相關(guān),也就是說(shuō),這些材料不僅具備AIE效應(yīng),而且還具備晶體發(fā)光增強(qiáng)(CEE)特性。2.通過(guò)TPE-NH2與5-硝基水楊醛反應(yīng)合成希夫堿NSTPE。由于硝基的強(qiáng)吸電子性質(zhì),化合物NSTPE具有明顯的溶劑效應(yīng)。從NSTPE的密度泛函理論計(jì)算可以發(fā)現(xiàn)其具有明顯的分子內(nèi)電荷轉(zhuǎn)移傾向。在聚集誘導(dǎo)的過(guò)程中,其熒光變化展現(xiàn)的“開(kāi)-關(guān)-開(kāi)”現(xiàn)象,呈U型,展現(xiàn)了NSTPE的AIE和分子內(nèi)扭曲電荷轉(zhuǎn)移性質(zhì)(TICT)性質(zhì)。除此之外,當(dāng)用不同溶劑重結(jié)晶時(shí),會(huì)得到不同固體顏色及不同的熒光發(fā)射波長(zhǎng)的NSTPE。通過(guò)研磨不同溶劑中重結(jié)晶出來(lái)的固體,它們會(huì)同時(shí)變成另外一種顏色,在經(jīng)過(guò)二氯甲烷熏蒸過(guò)后,研磨后的固體粉末的顏色又恢復(fù)到原來(lái)的顏色,即NSTPE具有壓致變色的性質(zhì)。通過(guò)測(cè)試三種顏色下的固體粉末的熒光發(fā)射光譜和XRD光譜進(jìn)一步證實(shí)了壓致變色性質(zhì)的結(jié)論。3.通過(guò)TPE-NH2與5-甲氧基水楊醛,香草醛,3-乙氧基鄰羥基苯醛反應(yīng)合成了三種希夫堿。發(fā)現(xiàn)三個(gè)化合物都具有ESIPT性質(zhì)。當(dāng)用紫外光刺激它們的固體粉末時(shí),三個(gè)化合物均立刻由原本的淡黃色變成紅色,在室溫下經(jīng)過(guò)20 min-2 h不等的時(shí)間又會(huì)由紅色變回原來(lái)的顏色。三種希夫堿分子都有羥基氫,所以在激發(fā)狀態(tài)下較容易發(fā)生分子內(nèi)的質(zhì)子轉(zhuǎn)移。通過(guò)測(cè)試三個(gè)化合物在不同顏色下的漫反射光譜來(lái)驗(yàn)證化合物由醇結(jié)構(gòu)到酮式結(jié)構(gòu)的轉(zhuǎn)變。
[Abstract]:The fluorescence emission wavelength and intensity of AIEs are changed due to the changes of the distorted conformation and stacking morphology in the solid or aggregated state. It has a wide application prospect in the fields of organic light-emitting diode (OLED), fluorescent biological probe and so on. As a typical aggregation-induced luminescent substance, Tetrastyrene (TPE) has attracted much attention in recent years. In this paper, eight Schiff bases were designed and synthesized by the reaction of tetrastyrene with a series of salicylidene derivatives, and their photophysical and photochemical properties were studied systematically. The mechanisms and applications of crystallization induced luminescence enhanced CEE(crystallization enhanced emission, intramolecular twisted charge transfer (TICTT), pressure-induced chromotropic piezoelectric (Piezallochromy), excited intramolecular proton transfer (ESIPT) and so on have been preliminarily explored. The specific research results are as follows: 1. A series of salicylaldehyde derivatives were synthesized from tetrastyrene as substrate and salicylaldehyde as substrate. Four Schiff base molecules were synthesized by condensation of tetrastyreneamine with salicylidene 5-bromosalicylaldehyde and 5-chlorosalicylaldehydes via aldehyde-amine condensation respectively, corresponding to compounds 1 to 4, respectively. By studying the optical properties of the target product, it is found that the fluorescence of the mixed solution increases with the increase of the water component when the unfavorable solvent water is added to THF, that is to say, the four Schiff bases have agglomeration induced luminescence enhancement properties. It was found that the fluorescence intensity of the mixed solution of compounds 2C _ 3 and 4 was obviously enhanced and the maximum emission wavelength was blue shift when the mixture solution was stationary for a period of time. The aggregation state luminescence of this series of compounds can be attributed to the crystallization of aggregates. The time dependence of this change is related to the rate of crystallization and the degree of crystallization, that is, these materials not only have AIE effect, but also have the properties of crystal luminescence enhanced CEE. 2. Schiff base NSTPE was synthesized by the reaction of TPE-NH2 with 5-nitrosalicylic aldehyde. Because of the strong electron absorption properties of nitro compounds, compound NSTPE has obvious solvent effect. From the density functional theory (DFT) of NSTPE, it can be found that it has obvious intramolecular charge transfer tendency. In the process of aggregation induction, the fluorescence changes of NSTPE show the "on-open" phenomenon, which shows the AIE of NSTPE and the character of intramolecular twisted charge transfer (TICTs). In addition, when recrystallized in different solvents, NSTPEs with different solid colors and different emission wavelengths can be obtained. By grinding the recrystallized solids in different solvents, they will change into another color at the same time. After fumigation with dichloromethane, the color of the ground solid powder will return to its original color, that is, NSTPE has the properties of pressure-induced discoloration. The results of fluorescence emission spectra and XRD spectra of the solid powders under three colors further confirmed the conclusion of pressure-chromic properties. Three Schiff bases were synthesized by the reaction of TPE-NH2 with 5-methoxy salicylic aldehyde and vanillin 3-ethoxy o-hydroxybenzaldehyde. It was found that all three compounds had ESIPT properties. When the solid powder was stimulated by ultraviolet light, the three compounds immediately changed from light yellow to red, and after 20 min-2 h at room temperature, the three compounds changed from red to original color. All the three Schiff base molecules have hydroxy hydrogen, so the intramolecular proton transfer is easy to occur in the excited state. The diffuse reflectance spectra of three compounds in different colors were tested to verify the transition from alcohol structure to ketone structure.
【學(xué)位授予單位】：中國(guó)礦業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O621.3

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