本文選題：激發(fā)態(tài)分子內(nèi)質(zhì)子轉(zhuǎn)移 + 2-(2-羥苯基)苯并噻唑�。� 參考：《西北農(nóng)林科技大學(xué)》2017年碩士論文

【摘要】：基于激發(fā)態(tài)分子內(nèi)質(zhì)子轉(zhuǎn)移(ESIPT)的熒光傳感器由于其雙波長(zhǎng)比率檢測(cè)、較大的斯托克斯(Stokes)位移等特性引起了人們廣泛關(guān)注,并在熒光探針、發(fā)光材料、激光染料、紫外過濾等方面得以廣泛應(yīng)用。然而,分子內(nèi)氫鍵的強(qiáng)度對(duì)于ESIPT熒光分子的光物理性質(zhì)具有決定性的影響,并且ESIPT熒光分子的發(fā)光特性容易受外界因素的影響。另外,一般的有機(jī)熒光染料具有聚集誘導(dǎo)淬滅的特點(diǎn),從而限制了其在許多方面的應(yīng)用。近幾年來具有高熒光量子產(chǎn)率(Фf)的固體熒光有機(jī)材料得到了人們廣泛的關(guān)注。本研究通過Sonogashira-偶聯(lián)反應(yīng)合成一系列以碳碳三鍵為連接臂的基于2-(2-羥苯基)苯并噻唑(HBT)衍生物ESIPT的分子,在苯酚環(huán)5’位修飾不同哈米特常數(shù)(σ)的取代基。利用紫外-可見吸收光譜和熒光光譜初步研究取代基對(duì)ESIPT熒光分子的發(fā)光性質(zhì)影響。實(shí)驗(yàn)數(shù)據(jù)顯示σ越大的HBT衍生物其分子內(nèi)氫鍵越強(qiáng),這使得其受外部因素破壞的可能性越小,酮式發(fā)射越強(qiáng),熒光發(fā)射藍(lán)移,量子產(chǎn)率越大。理論計(jì)算和晶體分析與實(shí)驗(yàn)結(jié)果相吻合。更為重要的是,甲氧�；c氰基修飾的兩個(gè)HBT衍生物不像其他的HBT衍生物和母體HBT在磷酸沖液中表現(xiàn)出陰離子發(fā)射,而是表現(xiàn)出酮式發(fā)射。這一研究結(jié)果為設(shè)計(jì)可應(yīng)用于生物醫(yī)學(xué)方面的新型ESIPT染料提供了一定的實(shí)驗(yàn)和理論方面的指導(dǎo)。另外,通過簡(jiǎn)單的Suzuki偶聯(lián)反應(yīng)合成兩個(gè)以碳碳雙鍵為連接臂的HBT衍生物:苯乙烯基修飾的HBT(HBT-s-Ph)和二苯乙烯基修飾的HBT(HBT-d-Ph)。在甲苯溶劑中,由于HBT-s-Ph的分子內(nèi)氫鍵強(qiáng)于的HBT-d-Ph,其Фf比HBT-d-Ph的稍微大一些;但在晶體形態(tài)下,它們的Фf均有明顯的提高,且HBT-d-Ph的Фf高達(dá)78%,是HBT-s-Ph的兩倍。晶體結(jié)構(gòu)表明HBT-d-Ph的發(fā)射顯著增強(qiáng),是由于垂直苯基導(dǎo)致獨(dú)特的堆積模式引起的。因此,這種設(shè)計(jì)方法有望被應(yīng)用到制備光學(xué)顯示器上的高性能發(fā)光與傳感材料、生物與學(xué)成像等方面。
[Abstract]:The fluorescence sensor based on excited intramolecular proton transfer spectroscopy (ESIPT) has attracted much attention due to its dual wavelength ratio detection, large Stokes Stokes shift and so on, and has attracted much attention in fluorescent probes, luminescent materials, laser dyes, and so on. Ultraviolet filtration has been widely used. However, the intensity of intramolecular hydrogen bonds has a decisive effect on the photophysical properties of ESIPT fluorescence molecules, and the luminescence properties of ESIPT fluorescence molecules are easily affected by external factors. In addition, general organic fluorescent dyes have the characteristics of agglomeration induced quenching, which limits their applications in many fields. In recent years, solid fluorescent organic materials with high fluorescence quantum yield (F) have been paid more and more attention. In this study, we synthesized a series of ESIPT derivatives based on 2-dihydroxyphenyl) benzothiazolium (HBT) derivatives by Sonogashira-coupling reaction, and modified the substituents of different Hammett constants (蟽) at the 5 'site of phenol ring. The effects of substituents on the luminescence properties of ESIPT fluorescence molecules were studied by UV-Vis absorption and fluorescence spectra. The experimental data show that the larger the 蟽, the stronger the intramolecular hydrogen bond of the HBT derivatives, which makes it less likely to be destroyed by external factors, the stronger the ketone emission is, the more blue the fluorescence emission is, and the higher the quantum yield is. The theoretical calculation and crystal analysis are in agreement with the experimental results. More importantly, the two HBT derivatives modified by methoxy and cyanoyl do not exhibit anion emission in phosphoric acid solution, but ketone emission, unlike other HBT derivatives and parent HBT. The results provide some experimental and theoretical guidance for the design of new ESIPT dyes for biomedical applications. In addition, two HBT derivatives were synthesized by simple Suzuki coupling reaction: styrene-modified HBTT-s-Phand and diphenyl vinyl-modified HBT-d-Phine. In toluene solvent, because the intramolecular hydrogen bond of HBT-s-Ph is stronger than that of HBT-d-Phand, its F is slightly larger than that of HBT-d-Ph, but in crystal morphology, its F is obviously increased, and the HBT-d-Ph has the highest F of 78, which is twice as high as that of HBT-s-Ph. The crystal structure indicates that the emission of HBT-d-Ph increases significantly due to the unique stacking pattern of perpendicular phenyl. Therefore, this design method is expected to be applied to the fabrication of high performance luminescent and sensing materials, biological and scientific imaging on optical displays.
【學(xué)位授予單位】：西北農(nóng)林科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O626.25

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