本文選題：TPE + AIE�。� 參考：《中國礦業(yè)大學》2017年碩士論文

【摘要】：聚集誘導發(fā)光(AIE)物質(zhì)在固態(tài)或者聚集狀態(tài)下,因為扭曲構象、堆積形態(tài)等變化導致其熒光發(fā)射的波長和強度發(fā)生改變,使其在有機發(fā)光二極管(OLED)、熒光生物探針等領域具有廣闊的應用前景。作為典型聚集誘導發(fā)光物質(zhì)的四苯乙烯(TPE),近些年來引起了人們廣泛的關注。本論文以希夫堿為結構中心,利用四苯乙烯與一系列水楊醛衍生物反應,設計合成八種希夫堿,并對它們的光物理光化學性質(zhì)進行了較為系統(tǒng)的研究。初步探索了相關化合物的結晶誘導發(fā)光增強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)等機理和應用。具體研究結果如下: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-氰基水楊醛通過醛胺縮合反應合成四種希夫堿分子,分別對應為化合物1至化合物4。通過研究目標產(chǎn)物的光學性質(zhì)發(fā)現(xiàn),在四氫呋喃(THF)中加入不良溶劑水時,隨著水組分的增加,混合溶液的熒光逐漸增強,也就是說四種希夫堿均具有聚集誘導發(fā)光增強性質(zhì)。當含水的混合溶液靜置一段時間后,發(fā)現(xiàn)化合物2,3和4的混合溶液熒光強度相比與靜置前,發(fā)生了明顯的增強,且最大發(fā)射波長也發(fā)生了藍移。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晶化。這種變化的時間依賴性與分子結晶速度和結晶化程度相關,也就是說,這些材料不僅具備AIE效應,而且還具備晶體發(fā)光增強(CEE)特性。2.通過TPE-NH2與5-硝基水楊醛反應合成希夫堿NSTPE。由于硝基的強吸電子性質(zhì),化合物NSTPE具有明顯的溶劑效應。從NSTPE的密度泛函理論計算可以發(fā)現(xiàn)其具有明顯的分子內(nèi)電荷轉(zhuǎn)移傾向。在聚集誘導的過程中,其熒光變化展現(xiàn)的“開-關-開”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,當用不同溶劑重結晶時,會得到不同固體顏色及不同的熒光發(fā)射波長的NSTPE。通過研磨不同溶劑中重結晶出來的固體,它們會同時變成另外一種顏色,在經(jīng)過二氯甲烷熏蒸過后,研磨后的固體粉末的顏色又恢復到原來的顏色,即NSTPE具有壓致變色的性質(zhì)。通過測試三種顏色下的固體粉末的熒光發(fā)射光譜和XRD光譜進一步證實了壓致變色性質(zhì)的結論。3.通過TPE-NH2與5-甲氧基水楊醛,香草醛,3-乙氧基鄰羥基苯醛反應合成了三種希夫堿。發(fā)現(xiàn)三個化合物都具有ESIPT性質(zhì)。當用紫外光刺激它們的固體粉末時,三個化合物均立刻由原本的淡黃色變成紅色,在室溫下經(jīng)過20 min-2 h不等的時間又會由紅色變回原來的顏色。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。通過測試三個化合物在不同顏色下的漫反射光譜來驗證化合物由醇結構到酮式結構的轉(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.
【學位授予單位】：中國礦業(yè)大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O621.3

【參考文獻】

相關期刊論文 前7條

1 劉曉;王濤;張晨;宋憲根;寧麗麗;丁云杰;;Co(Ⅱ)-席夫堿配合物在水溶液中催化苯甲醇氧化制苯甲醛的研究[J];石油化工;2015年12期

2 季春;周鳳麗;司玲;;一類鄰甲氧基苯乙酸類席夫堿的合成及抑菌活性研究[J];南京師大學報(自然科學版);2015年02期

3 郭海福;潘勇;馬德運;閆鵬;;吸電子基團對席夫堿及其鈀配合物在抑菌及催化活性方面的影響[J];無機化學學報;2013年07期

4 閆繼明;秦安軍;孫景志;唐本忠;;聚集誘導發(fā)光分子在生物檢測領域的應用[J];科學通報;2010年13期

5 高宇;張月成;趙繼全;;雙氮席夫堿配體對甲基三氧化錸催化烯烴環(huán)氧化反應的影響[J];催化學報;2009年12期

6 錢立軍;支俊格;佟斌;楊帆;趙瑋;董宇平;;具有聚集誘導發(fā)光性質(zhì)的化合物[J];化學進展;2008年05期

7 錢妍;解令海;王雙清;楊國強;;聚集誘導的熒光增強體系研究進展[J];南京郵電大學學報(自然科學版);2008年01期

，

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