氰基二苯乙烯衍生物的合成与聚集体发光行为
发布时间：2018-07-28 07:01
【摘要】：有机小分子发光材料具有结构容易确定,产物容易分离,易修饰和自组装性质优良等特点,引起了人们广泛的研究兴趣。然而,由于存在较强的分子间相互作用和电荷转移,固态分子间容易聚集,使发光效率减小和亮度降低,导致荧光猝灭。近年来,报道了许多性能优异的有机小分子发光材料,特别是聚集诱导发光(aggregation-induced emission,AIE)材料和聚集诱导发光增强(aggregation-induced emission enhancement,AIEE)材料的报道,为设计、合成具有优异固态发光性质的材料提供了有效的思路。但是,大多数AIE/AIEE材料固体发光效率仍不理想,聚集体结构与发光性质之间的关系还有待进一步探讨。氰基取代二苯乙烯衍生物是典型的AIEE基团,其具有聚集体发光性质优良,合成简单和自组装形式多样等优良性质,为开发聚集体发光性质优良的材料,探讨聚集体结构与性质的相关性提供了有利条件。本文在充分文献调研的基础上,设计合成了一系列具有优良聚集态发光性能的氰基取代二苯乙烯衍生物,通过光谱分析、晶体结构解析和理论计算,研究了分子聚集体结构与材料性质的相关性,探讨了化合物聚集态发光机理。同时,根据材料的结构特点和性质差异,实现了发光波段的调节,探索了材料在发光液晶和荧光探针领域的应用。主要研究内容如下:1、阴离子调控分子聚集体结构与聚集态发光有机盐类化合物在分子聚集结构调控方面具有独特的优势,它们光物理性质的调节可以通过改变阳离子和阴离子实现。本文设计、合成了四个含不同阴离子的氰基苯乙烯吡啶嗡盐化合物(PyCl,PyNO3,PyOTs,PyPh4B),研究了阴离子的改变对其结构和性质的影响。在稀有机溶液中,化合物处于游离态,由于它们具有相同的阳离子生色团,阴离子的改变对其光物理性质影响不大。然而,在固体态它们却表现出不同发光性质。随着阴离子体积的增大,由Cl-、N03-到OTs-,化合物的发光逐渐蓝移,由浅绿色变为深蓝色,荧光量子产率由2.5%增加到13.1%,然而体积最大的Ph4B-离子吡啶盐却没有固态荧光发射。单晶结构解析和DFT理论计算结果表明,化合物固体态发光是由于阳离子二聚体(dimer)形成,而Ph4B-离子较大的空间位阻作用,阻碍了阳离子dimer的形成,因此PyPh4B固体没有荧光发射。同时,这种独特的排列方式使化合物PyNO3具有晶体面各向异性荧光性质。2、侧链调控分子聚集体结构与聚集态发光非共轭基团的变化能够影响分子的堆积方式,改变聚集体的结构,从而调节化合物的聚集态发光。以氰基二苯乙烯为母体,分别通过"一锅法"简洁高效地合成了一系列D-π-A型含不同侧链的氰基二苯乙烯衍生物(ZH,ZOM,ZOE,ZOB),对其结构进行了全面的表征。通过紫外可见吸收光谱和荧光发射光谱研究了侧链对化合物游离态和聚集态光物理性质的影响,结果表明侧链对化合物游离态的光物理性质影响不大,对化合物聚集态性质有较大影响。未进行侧链修饰的ZH在游离态和聚集态发光都很弱,修饰侧链的ZOM,ZOE和ZOB表现出AIEE性质,在溶液中发光很弱,聚集态荧光增强。进一步生长了四个化合物的单晶,通过结构分析研究了侧链对化合物聚集体结构的影响以及结构与性质的相关性,结果表明化合物ZH分子π体系之间没有相互作用,修饰侧链后,化合物ZOM形成H-dimer聚集体,ZOM和ZOB形成J-聚集体,H-dimer和J-聚集体的形成扩大了π电子的离域范围,使化合物聚集态发光增强。3、末端烷基链调控分子聚集态发光与液晶性质开发发光性质优良的液晶材料能够解决液晶器件不能主动发光的问题,从而简化器件结构,降低生产成本,同时降低能耗,提高对比度和亮度。吲哚[3,2b]咔唑具有优异的发光性能,本文通过将氰基二苯乙烯单元和吲哚[3,2b]咔唑基团引入到一个分子中,并调节改变分子末端烷基链长度,设计合成了三个含不同末端烷基链的氰基二苯乙烯吲哚[3,2b]咔唑衍生物(ZY4,ZY8,ZY12),表征了化合物结构,研究了末端烷基链不同对化合物游离态和聚集态光物理性质以及液晶性质的影响。结果表明:末端烷基链对化合物单分子的光物理性质影响不大,但影响化合物聚集态发光。三个化合物都具有AIEE性质,随着末端烷基链的增长,固体的发光波长红移,量子产率逐渐升高。ZY12具有液晶性质,随着偏振角度的变化,其表现出发光各向异性。同时,在电场作用下,ZY12液晶器件发光减弱,有作为电场响应器件的潜力。4、Hg~(2+)诱导分子聚集荧光探针的设计与合成利用氰基二苯乙烯化合物的AIEE性质,引入金属螯合能力较强的席夫碱结构单元,基于分子内或分子间聚集荧光增强,设计合成了两个席夫碱修饰的氰基二苯乙烯衍生物(TS,Z1)荧光探针。两个化合物都具有AIEE性质,在水环境中不会因聚集产生荧光猝灭。通过紫外可见吸收光谱和荧光光谱研究探针分子基本的光物理性质和离子识别性质。由于探针TS和Z1分子较强的金属离子螯合作用,探针分子与Hg~(2+)发生螯合聚集,增强荧光发射,从而实现对水环境中Hg~(2+)的荧光"turn-on"识别。同时,利用荧光共聚焦显微镜技术,化合物Z1可以有效检测HepG2细胞中的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.
【学位授予单位】：安徽大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：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.
【学位授予单位】：安徽大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TQ422
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