本文選題：聚集誘導(dǎo)發(fā)光　切入點(diǎn)：激基締合物　出處：《西北農(nóng)林科技大學(xué)》2017年碩士論文　論文類(lèi)型：學(xué)位論文

【摘要】：近年來(lái),有機(jī)熒光材料在光化學(xué)研究領(lǐng)域和光電子設(shè)備領(lǐng)域引起了廣泛的關(guān)注,特別是具有刺激響應(yīng)的熒光材料。由于很多應(yīng)用于實(shí)際的有機(jī)熒光材料都是以固態(tài)或薄膜狀態(tài)存在,因此化合物在聚集態(tài)就需要具有較高的熒光量子產(chǎn)率。但是,一般的有機(jī)發(fā)光化合物在稀溶液具有較高的熒光效率,一旦形成聚集態(tài)熒光就會(huì)急劇減弱甚至直接淬滅,這就是所謂的“聚集誘導(dǎo)猝滅現(xiàn)象(ACQ)”。很多科研工作者最初使用一些方法使其在聚集態(tài)不再猝滅,但最終的結(jié)果都不是很理想。直到發(fā)現(xiàn)聚集誘導(dǎo)發(fā)光(AIE)現(xiàn)象,才給固態(tài)熒光材料的設(shè)計(jì)和合成提供了新的思路。近些年發(fā)展起來(lái)的刺激響應(yīng)型有機(jī)固體熒光智能材料在信息存貯、防偽、安全墨水等領(lǐng)域展示出非常大的潛在用途。本課題組前期研究顯示,芴酮類(lèi)分子在AIE和刺激響應(yīng)的熒光轉(zhuǎn)換方面展現(xiàn)出優(yōu)良的性能。本論文在前期研究基礎(chǔ)之上,對(duì)芴酮單元進(jìn)行結(jié)構(gòu)改進(jìn)與擴(kuò)展,設(shè)計(jì)合成了一系列新型的AIE分子和刺激響應(yīng)的固體熒光轉(zhuǎn)換分子,并著重研究了它們的AIE機(jī)理及其結(jié)構(gòu)與性能之間的關(guān)系,取得了如下創(chuàng)新性的成果:1.設(shè)計(jì)合成了四種芳基取代的芴酮化合物,分別為DPF、PDOF、DDOF和NDOF,這些化合物具有典型的AIE性質(zhì),并且具有較高的熒光量子產(chǎn)率。在分子聚集的過(guò)程中,熒光強(qiáng)度逐漸增強(qiáng)的同時(shí)還伴隨著約160 nm的紅移。我們通過(guò)單晶結(jié)構(gòu)和理論計(jì)算揭示了AIE機(jī)理。在分子堆積圖中,我們發(fā)現(xiàn)每?jī)蓚�(gè)分子之間通過(guò)氫鍵形成二聚體,激發(fā)后形成激基締合物。我們認(rèn)為紅移現(xiàn)象來(lái)源于激基締合物。另外,光譜特征顯示了化合物PDOF、DDOF和NDOF相較于DPF更容易形成激基締合物。2.設(shè)計(jì)合成了四個(gè)對(duì)稱和不對(duì)稱的噻吩取代芴酮衍生物,分別為CTPF、ATPF、BTPF和ETPF。這四個(gè)化合物都具有高的熒光量子產(chǎn)率和典型的AIE性質(zhì)。分子聚集過(guò)程不僅僅使熒光發(fā)射峰增強(qiáng),還使發(fā)射峰的位置相對(duì)于它們的單分子發(fā)射峰來(lái)說(shuō)有170 nm的紅移。單晶結(jié)構(gòu)表明,上下兩個(gè)臨近的分子通過(guò)π-π相互作用形成一個(gè)靜態(tài)的激基締合物,我們認(rèn)為紅移現(xiàn)象主要來(lái)源于靜態(tài)激基締合物的形成。另外,我們通過(guò)收集ATPF單分子和ATPF二聚體的分子軌道能量,理論計(jì)算結(jié)果與吸收光譜和發(fā)射光譜數(shù)據(jù)吻合。3.設(shè)計(jì)合成了芴類(lèi)化合物MDPF,此化合物在溶液中和固體條件下均展示了高的發(fā)光效率。通過(guò)溶劑緩慢揮發(fā)法和溶劑分層法培養(yǎng)單晶,最終得到三種具有不同熒光發(fā)射的單晶G-MDPF、B-MDPF和V-MDPF。其中藍(lán)色的B-MDPF通過(guò)加熱可以變成紫色,而黃色的G-MDPF通過(guò)加熱可以變?yōu)樗{(lán)色。通過(guò)XRD數(shù)據(jù)可知,相互變色過(guò)程是晶相與晶相之間的轉(zhuǎn)變。為了探究熒光轉(zhuǎn)換機(jī)理,我們解析單晶結(jié)構(gòu)得知,不同顏色的單晶內(nèi)部是不同的堆積模式,存在不同的激發(fā)下的電荷轉(zhuǎn)移途徑,導(dǎo)致其不同的熒光顏色。
[Abstract]:In recent years, organic fluorescent materials have attracted wide attention in the field of photochemistry and optoelectronic equipment. Because many of the organic fluorescent materials used in practical applications exist in solid or thin film state, it is necessary for the compounds to have high fluorescence quantum yield in the aggregate state. The general organic luminescent compounds have high fluorescence efficiency in dilute solution, and once they form the aggregate state, the fluorescence will weaken sharply or even be quenched directly. This is the so-called "agglomeration induced quenching phenomenon". Many researchers initially used methods to make it no longer quench in the aggregate state, but the end result was not ideal. Until the AIE-induced aggregation phenomenon was discovered, It provides a new idea for the design and synthesis of solid-state fluorescent materials. In recent years, stimulus-responsive organic solid-state fluorescent smart materials are stored in information, and anti-counterfeiting. Safety ink and other fields show great potential applications. Our previous studies show that fluorenone molecules exhibit excellent performance in AIE and fluorescence conversion of stimuli response. A series of novel AIE molecules and stimulus-responsive solid-state fluorescence conversion molecules were designed and synthesized by improving and extending the structure of fluorenone units. The AIE mechanism and the relationship between structure and properties of these molecules were studied. Four aryl substituted fluorenone compounds were designed and synthesized. They are DPFN PDOFN DDOF and NDOF respectively. These compounds have typical AIE properties and high fluorescence quantum yield. The fluorescence intensity is gradually enhanced and accompanied by a red shift of about 160nm. We reveal the mechanism of AIE by single crystal structure and theoretical calculation. In the molecular stacking diagram, we find that the dimer is formed by hydrogen bonding between every two molecules. We think that the red shift phenomenon comes from the excimer association complex. In addition, Spectral characteristics show that the compounds PDOF-DDOF and NDOF are more likely to form excimer complexes than DPF compounds. Four symmetric and asymmetric thiophene substituted fluorenone derivatives have been designed and synthesized. These four compounds have high fluorescence quantum yield and typical AIE properties. The molecular aggregation process not only enhances the fluorescence emission peak, but also increases the fluorescence emission peak. The position of the emission peaks is also red shifted by 170 nm relative to their monolayer emission peaks. The single crystal structure indicates that the upper and lower adjacent molecules form a static excimer by 蟺-蟺 interaction. We believe that the redshift is mainly due to the formation of static excimer complexes. In addition, we collect the molecular orbital energy of ATPF monolayers and ATPF dimers. The theoretical calculation results are in agreement with the absorption and emission spectra data. 3. The fluorene compound MDPFs have been designed and synthesized. The compounds exhibit high luminescence efficiency under the conditions of solution and solid. The single crystals are grown by solvent slow volatilization method and solvent stratification method. Finally, three kinds of single crystals with different fluorescence emission, G-MDPF B-MDPF and V-MDPPF, were obtained. The blue B-MDPF can become purple by heating, and the yellow G-MDPF can change to blue by heating. In order to study the mechanism of fluorescence conversion, we have analyzed the structure of single crystal and found that there are different stacking modes in different color single crystals, and there are different charge transfer pathways under different excitations. Causes its different fluorescence color.
【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(lèi)號(hào)】：O621.22

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本文編號(hào)：1602380