氰基二苯乙烯衍生物的合成與聚集體發(fā)光行為
發(fā)布時(shí)間：2018-07-28 07:01
【摘要】：有機(jī)小分子發(fā)光材料具有結(jié)構(gòu)容易確定,產(chǎn)物容易分離,易修飾和自組裝性質(zhì)優(yōu)良等特點(diǎn),引起了人們廣泛的研究興趣。然而,由于存在較強(qiáng)的分子間相互作用和電荷轉(zhuǎn)移,固態(tài)分子間容易聚集,使發(fā)光效率減小和亮度降低,導(dǎo)致熒光猝滅。近年來,報(bào)道了許多性能優(yōu)異的有機(jī)小分子發(fā)光材料,特別是聚集誘導(dǎo)發(fā)光(aggregation-induced emission,AIE)材料和聚集誘導(dǎo)發(fā)光增強(qiáng)(aggregation-induced emission enhancement,AIEE)材料的報(bào)道,為設(shè)計(jì)、合成具有優(yōu)異固態(tài)發(fā)光性質(zhì)的材料提供了有效的思路。但是,大多數(shù)AIE/AIEE材料固體發(fā)光效率仍不理想,聚集體結(jié)構(gòu)與發(fā)光性質(zhì)之間的關(guān)系還有待進(jìn)一步探討。氰基取代二苯乙烯衍生物是典型的AIEE基團(tuán),其具有聚集體發(fā)光性質(zhì)優(yōu)良,合成簡(jiǎn)單和自組裝形式多樣等優(yōu)良性質(zhì),為開發(fā)聚集體發(fā)光性質(zhì)優(yōu)良的材料,探討聚集體結(jié)構(gòu)與性質(zhì)的相關(guān)性提供了有利條件。本文在充分文獻(xiàn)調(diào)研的基礎(chǔ)上,設(shè)計(jì)合成了一系列具有優(yōu)良聚集態(tài)發(fā)光性能的氰基取代二苯乙烯衍生物,通過光譜分析、晶體結(jié)構(gòu)解析和理論計(jì)算,研究了分子聚集體結(jié)構(gòu)與材料性質(zhì)的相關(guān)性,探討了化合物聚集態(tài)發(fā)光機(jī)理。同時(shí),根據(jù)材料的結(jié)構(gòu)特點(diǎn)和性質(zhì)差異,實(shí)現(xiàn)了發(fā)光波段的調(diào)節(jié),探索了材料在發(fā)光液晶和熒光探針領(lǐng)域的應(yīng)用。主要研究?jī)?nèi)容如下:1、陰離子調(diào)控分子聚集體結(jié)構(gòu)與聚集態(tài)發(fā)光有機(jī)鹽類化合物在分子聚集結(jié)構(gòu)調(diào)控方面具有獨(dú)特的優(yōu)勢(shì),它們光物理性質(zhì)的調(diào)節(jié)可以通過改變陽(yáng)離子和陰離子實(shí)現(xiàn)。本文設(shè)計(jì)、合成了四個(gè)含不同陰離子的氰基苯乙烯吡啶嗡鹽化合物(PyCl,PyNO3,PyOTs,PyPh4B),研究了陰離子的改變對(duì)其結(jié)構(gòu)和性質(zhì)的影響。在稀有機(jī)溶液中,化合物處于游離態(tài),由于它們具有相同的陽(yáng)離子生色團(tuán),陰離子的改變對(duì)其光物理性質(zhì)影響不大。然而,在固體態(tài)它們卻表現(xiàn)出不同發(fā)光性質(zhì)。隨著陰離子體積的增大,由Cl-、N03-到OTs-,化合物的發(fā)光逐漸藍(lán)移,由淺綠色變?yōu)樯钏{(lán)色,熒光量子產(chǎn)率由2.5%增加到13.1%,然而體積最大的Ph4B-離子吡啶鹽卻沒有固態(tài)熒光發(fā)射。單晶結(jié)構(gòu)解析和DFT理論計(jì)算結(jié)果表明,化合物固體態(tài)發(fā)光是由于陽(yáng)離子二聚體(dimer)形成,而Ph4B-離子較大的空間位阻作用,阻礙了陽(yáng)離子dimer的形成,因此PyPh4B固體沒有熒光發(fā)射。同時(shí),這種獨(dú)特的排列方式使化合物PyNO3具有晶體面各向異性熒光性質(zhì)。2、側(cè)鏈調(diào)控分子聚集體結(jié)構(gòu)與聚集態(tài)發(fā)光非共軛基團(tuán)的變化能夠影響分子的堆積方式,改變聚集體的結(jié)構(gòu),從而調(diào)節(jié)化合物的聚集態(tài)發(fā)光。以氰基二苯乙烯為母體,分別通過"一鍋法"簡(jiǎn)潔高效地合成了一系列D-π-A型含不同側(cè)鏈的氰基二苯乙烯衍生物(ZH,ZOM,ZOE,ZOB),對(duì)其結(jié)構(gòu)進(jìn)行了全面的表征。通過紫外可見吸收光譜和熒光發(fā)射光譜研究了側(cè)鏈對(duì)化合物游離態(tài)和聚集態(tài)光物理性質(zhì)的影響,結(jié)果表明側(cè)鏈對(duì)化合物游離態(tài)的光物理性質(zhì)影響不大,對(duì)化合物聚集態(tài)性質(zhì)有較大影響。未進(jìn)行側(cè)鏈修飾的ZH在游離態(tài)和聚集態(tài)發(fā)光都很弱,修飾側(cè)鏈的ZOM,ZOE和ZOB表現(xiàn)出AIEE性質(zhì),在溶液中發(fā)光很弱,聚集態(tài)熒光增強(qiáng)。進(jìn)一步生長(zhǎng)了四個(gè)化合物的單晶,通過結(jié)構(gòu)分析研究了側(cè)鏈對(duì)化合物聚集體結(jié)構(gòu)的影響以及結(jié)構(gòu)與性質(zhì)的相關(guān)性,結(jié)果表明化合物ZH分子π體系之間沒有相互作用,修飾側(cè)鏈后,化合物ZOM形成H-dimer聚集體,ZOM和ZOB形成J-聚集體,H-dimer和J-聚集體的形成擴(kuò)大了π電子的離域范圍,使化合物聚集態(tài)發(fā)光增強(qiáng)。3、末端烷基鏈調(diào)控分子聚集態(tài)發(fā)光與液晶性質(zhì)開發(fā)發(fā)光性質(zhì)優(yōu)良的液晶材料能夠解決液晶器件不能主動(dòng)發(fā)光的問題,從而簡(jiǎn)化器件結(jié)構(gòu),降低生產(chǎn)成本,同時(shí)降低能耗,提高對(duì)比度和亮度。吲哚[3,2b]咔唑具有優(yōu)異的發(fā)光性能,本文通過將氰基二苯乙烯單元和吲哚[3,2b]咔唑基團(tuán)引入到一個(gè)分子中,并調(diào)節(jié)改變分子末端烷基鏈長(zhǎng)度,設(shè)計(jì)合成了三個(gè)含不同末端烷基鏈的氰基二苯乙烯吲哚[3,2b]咔唑衍生物(ZY4,ZY8,ZY12),表征了化合物結(jié)構(gòu),研究了末端烷基鏈不同對(duì)化合物游離態(tài)和聚集態(tài)光物理性質(zhì)以及液晶性質(zhì)的影響。結(jié)果表明:末端烷基鏈對(duì)化合物單分子的光物理性質(zhì)影響不大,但影響化合物聚集態(tài)發(fā)光。三個(gè)化合物都具有AIEE性質(zhì),隨著末端烷基鏈的增長(zhǎng),固體的發(fā)光波長(zhǎng)紅移,量子產(chǎn)率逐漸升高。ZY12具有液晶性質(zhì),隨著偏振角度的變化,其表現(xiàn)出發(fā)光各向異性。同時(shí),在電場(chǎng)作用下,ZY12液晶器件發(fā)光減弱,有作為電場(chǎng)響應(yīng)器件的潛力。4、Hg~(2+)誘導(dǎo)分子聚集熒光探針的設(shè)計(jì)與合成利用氰基二苯乙烯化合物的AIEE性質(zhì),引入金屬螯合能力較強(qiáng)的席夫堿結(jié)構(gòu)單元,基于分子內(nèi)或分子間聚集熒光增強(qiáng),設(shè)計(jì)合成了兩個(gè)席夫堿修飾的氰基二苯乙烯衍生物(TS,Z1)熒光探針。兩個(gè)化合物都具有AIEE性質(zhì),在水環(huán)境中不會(huì)因聚集產(chǎn)生熒光猝滅。通過紫外可見吸收光譜和熒光光譜研究探針分子基本的光物理性質(zhì)和離子識(shí)別性質(zhì)。由于探針TS和Z1分子較強(qiáng)的金屬離子螯合作用,探針分子與Hg~(2+)發(fā)生螯合聚集,增強(qiáng)熒光發(fā)射,從而實(shí)現(xiàn)對(duì)水環(huán)境中Hg~(2+)的熒光"turn-on"識(shí)別。同時(shí),利用熒光共聚焦顯微鏡技術(shù),化合物Z1可以有效檢測(cè)HepG2細(xì)胞中的Hg~(2+)。
[Abstract]:Organic small molecular luminescent materials have the characteristics of easy determination, easy separation of products, easy to modify and excellent self-assembly, which have aroused widespread interest in research. However, because of the strong intermolecular interaction and charge transfer, the solid-state molecules are easily aggregated, resulting in reduced luminescence efficiency and luminance, resulting in fluorescence quenching. In recent years, many excellent organic small molecular light-emitting materials have been reported, especially aggregation-induced emission (AIE) materials and aggregation-induced emission enhancement (AIEE) materials, which provide effective materials for the design of materials with excellent solid-state luminescence properties. However, the luminescence efficiency of most AIE/AIEE materials is still not ideal, and the relationship between the aggregate structure and the luminescent properties remains to be further discussed. The cyanic substituted two styrene derivatives are typical AIEE groups, which have excellent properties of aggregate luminescence, simple synthesis and various forms of self-assembly, for the development and aggregation. In this paper, a series of cyanoradical substituted two styrene derivatives with excellent aggregation state luminescence properties were designed and synthesized on the basis of sufficient literature investigation, and the molecules were studied by spectral analysis, crystal structure analysis and theoretical calculation on the basis of sufficient literature investigation. The correlation between the aggregate structure and the properties of material has been discussed. At the same time, according to the structural characteristics and properties of the materials, the modulation of the luminescent band is realized. The application of the material in the field of luminescent liquid crystal and fluorescence probe is explored. The main contents are as follows: 1, the aggregation structure and aggregation of the anion regulator. The luminescent organic salts have unique advantages in the regulation of molecular aggregation structure. Their photophysical properties can be regulated by changing cations and anions. In this paper, four cyanostyrene pyridine buzz compounds (PyCl, PyNO3, PyOTs, PyPh4B) containing different anions were synthesized and the changes of anions were studied. The effects on their structure and properties. In the rare machine solution, the compounds are in the free state. Because they have the same cationic chromophores, the changes of anions have little effect on their photophysical properties. However, they show different luminescent properties in the solid state. With the increase of the volume of anions, the hair of the compound is from Cl-, N03- to OTs-. The light green shifts from light green to dark blue, and the fluorescence quantum yield increases from 2.5% to 13.1%. However, the largest Ph4B- ion pyridinium salt has no solid fluorescence emission. Single crystal structure analysis and DFT theoretical calculation show that the solid state luminescence of the compound is formed by the cationic two polymer (dimer), while the space position of the Ph4B- ion is larger. Hindrance, which hinders the formation of cationic dimer, so the PyPh4B solid has no fluorescence emission. At the same time, this unique arrangement makes the compound PyNO3 have the crystal surface anisotropic fluorescence property.2. The modification of the aggregate structure of the side chain and the unconjugated group of the aggregation state of the luminescence can affect the accumulation of molecules and change the aggregates. A series of cyanic two styrene (ZH, ZOM, ZOE, ZOB) with different side chains (ZH, ZOM, ZOE, ZOB) were synthesized by "one pot method" by "one pot", and the structure was characterized by a "one pot" method. The UV visible absorption spectrum and fluorescence emission spectroscopic study were carried out. The effects of side chains on the photophysical properties of free and aggregation states are investigated. The results show that the side chains have little influence on the photophysical properties of the compounds free state, and have great influence on the properties of the compounds. The free and aggregation states of ZH without side chain modification are very weak, and the ZOM, ZOE and ZOB of the modified side chains exhibit AIEE properties. The luminescence is very weak in the solution, and the aggregation fluorescence is enhanced. The single crystal of four compounds is further grown. The effect of the side chain on the aggregate structure of the compound and the correlation between the structure and properties of the compound are studied by structure analysis. The results show that there is no interaction between the ZH molecule of the compound and the compound ZOM forms H-dimer polymerization after the modification of the side chain. Collectives, ZOM and ZOB form J- aggregates, and the formation of H-dimer and J- aggregates enlarges the delocalization range of the pi electrons and makes the aggregation luminescence of the compound enhance.3. The terminal alkyl chain regulates the molecular aggregation luminescence and the liquid crystal properties to develop the excellent luminescence properties of the liquid crystal devices to solve the problem that the liquid crystal devices can not give the active luminescence, thus simplifying the devices. Structure, reduce production cost, reduce energy consumption, increase contrast and brightness. Indole [3,2b] carbazole has excellent luminescence properties. By introducing cyanyl two styrene unit and indole [3,2b] carbazole group into one molecule and adjusting the length of alkyl chain at the end of the molecule, three different terminal alkyl chains are designed and synthesized. The cyanyl two styrene indole [3,2b] carbazole derivatives (ZY4, ZY8, ZY12) were used to characterize the structure of the compounds. The effects of the different terminal alkyl chains on the photophysical properties of the free and aggregated states of the compounds and the liquid crystal properties were investigated. The results showed that the terminal alkyl chain had little effect on the photophysical properties of the single molecule, but affected the aggregation state of the compound. The three compounds have the properties of AIEE. With the increase of the terminal alkyl chain, the luminescence wavelength of the solid is red shift and the quantum yield increases gradually.ZY12 has the liquid crystal property. With the change of the polarization angle, it shows the luminescence anisotropy. At the same time, under the action of the electric field, the luminescence of the ZY12 liquid crystal is weakened, and there is the potential of the electric field response device. .4, Hg~ (2+) induced molecular aggregation fluorescence probe is designed and synthesized using AIEE properties of cyanic two styrene compounds, introducing a strong metal chelating Schiff base structure unit. Based on intramolecular or intermolecular aggregation fluorescence enhancement, two Schiff base modified cyanic two styrene derivatives (TS, Z1) fluorescent probes are designed and synthesized. The compounds have the properties of AIEE, which can not produce fluorescence quenching in the water environment. The basic photophysical properties and ion recognition properties of the probe molecules are studied by UV visible absorption and fluorescence spectra. Because of the strong metal ion chelation of the probe TS and the Z1 molecules, the probe molecules are chelated and aggregated with Hg~ (2+), and the fluorescence is enhanced. Emission, thus realizing the identification of Hg~ (2+) fluorescence "turn-on" in water environment, and using fluorescence confocal microscope technique, compound Z1 can effectively detect Hg~ (2+) in HepG2 cells.
【學(xué)位授予單位】：安徽大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TQ422
[Abstract]:Organic small molecular luminescent materials have the characteristics of easy determination, easy separation of products, easy to modify and excellent self-assembly, which have aroused widespread interest in research. However, because of the strong intermolecular interaction and charge transfer, the solid-state molecules are easily aggregated, resulting in reduced luminescence efficiency and luminance, resulting in fluorescence quenching. In recent years, many excellent organic small molecular light-emitting materials have been reported, especially aggregation-induced emission (AIE) materials and aggregation-induced emission enhancement (AIEE) materials, which provide effective materials for the design of materials with excellent solid-state luminescence properties. However, the luminescence efficiency of most AIE/AIEE materials is still not ideal, and the relationship between the aggregate structure and the luminescent properties remains to be further discussed. The cyanic substituted two styrene derivatives are typical AIEE groups, which have excellent properties of aggregate luminescence, simple synthesis and various forms of self-assembly, for the development and aggregation. In this paper, a series of cyanoradical substituted two styrene derivatives with excellent aggregation state luminescence properties were designed and synthesized on the basis of sufficient literature investigation, and the molecules were studied by spectral analysis, crystal structure analysis and theoretical calculation on the basis of sufficient literature investigation. The correlation between the aggregate structure and the properties of material has been discussed. At the same time, according to the structural characteristics and properties of the materials, the modulation of the luminescent band is realized. The application of the material in the field of luminescent liquid crystal and fluorescence probe is explored. The main contents are as follows: 1, the aggregation structure and aggregation of the anion regulator. The luminescent organic salts have unique advantages in the regulation of molecular aggregation structure. Their photophysical properties can be regulated by changing cations and anions. In this paper, four cyanostyrene pyridine buzz compounds (PyCl, PyNO3, PyOTs, PyPh4B) containing different anions were synthesized and the changes of anions were studied. The effects on their structure and properties. In the rare machine solution, the compounds are in the free state. Because they have the same cationic chromophores, the changes of anions have little effect on their photophysical properties. However, they show different luminescent properties in the solid state. With the increase of the volume of anions, the hair of the compound is from Cl-, N03- to OTs-. The light green shifts from light green to dark blue, and the fluorescence quantum yield increases from 2.5% to 13.1%. However, the largest Ph4B- ion pyridinium salt has no solid fluorescence emission. Single crystal structure analysis and DFT theoretical calculation show that the solid state luminescence of the compound is formed by the cationic two polymer (dimer), while the space position of the Ph4B- ion is larger. Hindrance, which hinders the formation of cationic dimer, so the PyPh4B solid has no fluorescence emission. At the same time, this unique arrangement makes the compound PyNO3 have the crystal surface anisotropic fluorescence property.2. The modification of the aggregate structure of the side chain and the unconjugated group of the aggregation state of the luminescence can affect the accumulation of molecules and change the aggregates. A series of cyanic two styrene (ZH, ZOM, ZOE, ZOB) with different side chains (ZH, ZOM, ZOE, ZOB) were synthesized by "one pot method" by "one pot", and the structure was characterized by a "one pot" method. The UV visible absorption spectrum and fluorescence emission spectroscopic study were carried out. The effects of side chains on the photophysical properties of free and aggregation states are investigated. The results show that the side chains have little influence on the photophysical properties of the compounds free state, and have great influence on the properties of the compounds. The free and aggregation states of ZH without side chain modification are very weak, and the ZOM, ZOE and ZOB of the modified side chains exhibit AIEE properties. The luminescence is very weak in the solution, and the aggregation fluorescence is enhanced. The single crystal of four compounds is further grown. The effect of the side chain on the aggregate structure of the compound and the correlation between the structure and properties of the compound are studied by structure analysis. The results show that there is no interaction between the ZH molecule of the compound and the compound ZOM forms H-dimer polymerization after the modification of the side chain. Collectives, ZOM and ZOB form J- aggregates, and the formation of H-dimer and J- aggregates enlarges the delocalization range of the pi electrons and makes the aggregation luminescence of the compound enhance.3. The terminal alkyl chain regulates the molecular aggregation luminescence and the liquid crystal properties to develop the excellent luminescence properties of the liquid crystal devices to solve the problem that the liquid crystal devices can not give the active luminescence, thus simplifying the devices. Structure, reduce production cost, reduce energy consumption, increase contrast and brightness. Indole [3,2b] carbazole has excellent luminescence properties. By introducing cyanyl two styrene unit and indole [3,2b] carbazole group into one molecule and adjusting the length of alkyl chain at the end of the molecule, three different terminal alkyl chains are designed and synthesized. The cyanyl two styrene indole [3,2b] carbazole derivatives (ZY4, ZY8, ZY12) were used to characterize the structure of the compounds. The effects of the different terminal alkyl chains on the photophysical properties of the free and aggregated states of the compounds and the liquid crystal properties were investigated. The results showed that the terminal alkyl chain had little effect on the photophysical properties of the single molecule, but affected the aggregation state of the compound. The three compounds have the properties of AIEE. With the increase of the terminal alkyl chain, the luminescence wavelength of the solid is red shift and the quantum yield increases gradually.ZY12 has the liquid crystal property. With the change of the polarization angle, it shows the luminescence anisotropy. At the same time, under the action of the electric field, the luminescence of the ZY12 liquid crystal is weakened, and there is the potential of the electric field response device. .4, Hg~ (2+) induced molecular aggregation fluorescence probe is designed and synthesized using AIEE properties of cyanic two styrene compounds, introducing a strong metal chelating Schiff base structure unit. Based on intramolecular or intermolecular aggregation fluorescence enhancement, two Schiff base modified cyanic two styrene derivatives (TS, Z1) fluorescent probes are designed and synthesized. The compounds have the properties of AIEE, which can not produce fluorescence quenching in the water environment. The basic photophysical properties and ion recognition properties of the probe molecules are studied by UV visible absorption and fluorescence spectra. Because of the strong metal ion chelation of the probe TS and the Z1 molecules, the probe molecules are chelated and aggregated with Hg~ (2+), and the fluorescence is enhanced. Emission, thus realizing the identification of Hg~ (2+) fluorescence "turn-on" in water environment, and using fluorescence confocal microscope technique, compound Z1 can effectively detect Hg~ (2+) in HepG2 cells.
【學(xué)位授予單位】：安徽大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TQ422
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