本文選題：A-π-D-π-A型 + 近紅外熒光染料��； 參考：《太原理工大學(xué)》2017年碩士論文

【摘要】：近年來(lái),紅光及近紅外熒光染料在光電材料、生物成像、熒光探針、信息加密等方面都有巨大的應(yīng)用需求,而有機(jī)紅光及近紅外熒光染料具有分子結(jié)構(gòu)靈活易調(diào)控、摩爾吸光系數(shù)相對(duì)較高、生物相容性好、價(jià)格低廉等優(yōu)點(diǎn)而成為當(dāng)前科學(xué)研究的熱點(diǎn)。本論文設(shè)計(jì)合成了一系列分別以丙二腈、茚二酮和三氰基呋喃衍生物(TCF)為電子受體,以己基和異辛基為N-烷基取代的咔唑類(lèi)A-π-D-π-A型有機(jī)熒光染料(h-CPDM/i-CPDM、h-CPBI/iCPBI和h-CPBT/i-CPBT)。通過(guò)紫外-可見(jiàn)吸收光譜、熒光發(fā)射光譜和瞬態(tài)熒光光譜、x射線衍射、差示掃描量熱法及掃描電子顯微鏡等研究了染料在溶液及聚集態(tài)下的發(fā)光行為,包括溶劑化效應(yīng)、聚集誘導(dǎo)發(fā)光性質(zhì),以及機(jī)械響應(yīng)發(fā)光性質(zhì)。研究結(jié)果證明:1.隨著電子受體的吸電子能力增強(qiáng),分子HOMO能級(jí)變化不大,LUMO能級(jí)逐漸降低,導(dǎo)致分子能隙減小,發(fā)光顏色紅移。2.溶劑化效應(yīng):h-CPDM/i-CPDM和h-CPBI/i-CPBI均具有顯著的溶劑化效應(yīng),從非極性的正己烷到強(qiáng)極性的DMSO中,h-CPDM/i-CPDM的發(fā)光顏色覆蓋了從藍(lán)色到橘紅色,發(fā)光波長(zhǎng)分別紅移了49/68 nm;h-CPBI/i-CPBI的發(fā)光顏色覆蓋了從藍(lán)色到紅色,紅移波長(zhǎng)達(dá)到168/176 nm。這種顯著的溶劑化效應(yīng)歸因于它們固有的分子內(nèi)電荷轉(zhuǎn)移(Intramolecular Charge Transfer,ICT)性質(zhì)。3.聚集誘導(dǎo)發(fā)光性質(zhì):化合物h-CPDM/i-CPDM以及h-CPBI在四氫呋喃和水的混合溶液中,分子在J-聚集過(guò)程中π-π堆積作用較強(qiáng),所以都存在聚集熒光猝滅現(xiàn)象。而化合物i-CPBI因其異辛基支鏈的空間位阻較大以及咔唑基團(tuán)的剛性較強(qiáng),在聚集過(guò)程中抑制了分子的π-π堆積作用,同時(shí)限制了分子的自由旋轉(zhuǎn)而減少了非輻射途徑,所以表現(xiàn)出聚集誘導(dǎo)發(fā)光(Aggregation Induced Emission,AIE)性質(zhì)。4.機(jī)械響應(yīng)發(fā)光性質(zhì):以丙二腈為電子受體的h-CPDM和i-CPDM研磨前后樣品的熒光量子產(chǎn)率分別從0.9%(λmax 678 nm)和0.3%(λmax 661 nm)增加到8.7%(λmax 610nm)和25.6%(λmax 596 nm);以茚二酮為電子受體的h-CPBI和i-CPBI研磨前后樣品的熒光量子產(chǎn)率分別從0.6%(λmax 713 nm)和0.3%(λmax 648nm)增加到18.6%(λmax 625 nm)和29.4%(λmax 628 nm);以TCF為電子受體的h-CPBT和i-CPBT研磨前后樣品的熒光量子產(chǎn)率分別從0.82%(714nm)和0.85%(717 nm)增加到5.41%(729 nm)和5.27%(731 nm),均實(shí)現(xiàn)了機(jī)械力誘導(dǎo)的熒光“開(kāi)啟”。它們的XRD和DSC數(shù)據(jù)結(jié)果表明,通過(guò)機(jī)械研磨使得h-CPDM/i-CPDM和h-CPBI/i-CPBI的分子聚集態(tài)的有序性被打破,從而實(shí)現(xiàn)了熒光增強(qiáng)。熒光壽命結(jié)果也表明,研磨前后產(chǎn)生了相轉(zhuǎn)變過(guò)程。
[Abstract]:In recent years, red and near infrared fluorescent dyes have great applications in photoelectric materials, biological imaging, fluorescence probes, information encryption, etc., while organic red and near infrared fluorescent dyes have flexible molecular structure. The advantages of relatively high molar absorptivity, good biocompatibility and low price have become the focus of current scientific research. In this paper, a series of carbazoles A- 蟺 -D蟺 -A organic fluorescent dyes with malonitrile, ninhydrin and tricyanofuran derivatives as electron receptors and hexyl and isooctyl as N-alkyl substituents have been designed and synthesized, respectively. The luminescence behavior of dyes in solution and aggregation state was studied by UV-Vis absorption spectra, fluorescence emission spectra and transient fluorescence spectra, X-ray diffraction, differential scanning calorimetry and scanning electron microscope. Aggregation induced luminescence and mechanical response luminescence. The result of the study proves that 1: 1. With the enhancement of the electron absorption ability of the electron receptor, the energy level of the molecular HOMO decreases gradually, which leads to the decrease of the molecular energy gap and the red shift of the luminescence color. Solvation effect: h-CPDM / I-CPDM and h-CPBI/i-CPBI have significant solvation effects, ranging from nonpolar n-hexane to highly polar DMSO with luminous colors covering the range from blue to orange. The luminous wavelengths are redshift 49 / 68 nm / h ~ (h-CPBI / i-CPBI), respectively, and the red shift wavelength is 168 / 176nm ~ (-1), covering the color from blue to red. This remarkable solvation effect is attributed to their intrinsic intramolecular charge transfer Charge transfer property. Aggregation induced luminescence: in the mixed solution of tetrahydrofuran and water, the 蟺-蟺 accumulation of compounds h-CPDM/i-CPDM and h-CPBI is stronger in the process of J- aggregation, so there exists the phenomenon of fluorescence quenching of aggregation. Because of the large steric hindrance of isooctyl branched chain and the strong rigidity of carbazole group, the compound i-CPBI inhibited the 蟺-蟺 accumulation of molecule during the aggregation process, and limited the free rotation of molecule, thus reducing the non-radiation pathway. Therefore, the agglomeration induced luminescence Induced emission of AIE.4. Photoluminescence properties of mechanical response: fluorescence quantum yields of h-CPDM and i-CPDM samples with malonitrile as electron acceptor increased from 0.9g (位 max 678nm) and 0.3um (位 max 661nm) to 8.7 (位 max 610nm) and 25.6N / m (位 max 596nmm), respectively; h-CPBI and i-CPBI with ninhydrin as electron acceptor before grinding The fluorescence quantum yields of the samples increased from 0. 6 (位 max 713 nm) and 0. 3 (位 max 648 nm) to 18. 6 (位 max 625 nm) and 29. 4 (位 max 628 nm), respectively. The fluorescence quantum yields of h-CPBT and i-CPBT polished samples with TCF as electron acceptor increased from 0. 822 ~ 714 nm and 0. 85 ~ 717 nm to 5. 41 ~ 729 nm and 5. 27 ~ 731 nm respectively. The mechanically induced fluorescence is now on. Their XRD and DSC data show that the order of the molecular aggregates of h-CPDM/i-CPDM and h-CPBI/i-CPBI is broken by mechanical grinding, thus the fluorescence enhancement is realized. The fluorescence lifetime also shows that phase transition occurs before and after grinding.
【學(xué)位授予單位】：太原理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：TQ617.3

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