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类型 基础研究 预答辩日期 2017-11-24
开始(开题)日期 2016-04-15 论文结束日期 2017-05-08
地点 化工楼新楼315 论文选题来源 非立项    论文字数 5.1 (万字)
题目 基于聚集诱导发光(AIE)和分子内质子转移(ESIPT)效应有机材料的合成及性能研究
主题词 聚集诱导发光,激发态分子内质子转移,荧光探针,发光器件
摘要 聚集诱导发光(AIE)材料在聚集态或固态时,因其空间构象和分子排列方式等因素的变化,表现出独特的荧光增强现象。AIE材料的发现克服了传统荧光材料在聚集态或固态时荧光降低甚至完全淬灭的缺陷,在荧光分子探针、电致发光器件、液晶显示材料和智能记忆材料等领域表现出巨大的应用潜力,因而受到了广泛的关注。本文利用绿色易行的席夫碱反应等手段,设计、合成了一系列具有AIE活性的发光分子,并探索了它们在荧光传感和电致发光器件上的应用性能,具体内容体现在以下几个方面: 1、设计并合成了含有香豆素荧光团的席夫碱衍生物4-[[(7-hydroxy-4-methyl-2-oxo-2H-1-benzopyran-8-yl)methylene]amino]?benzoic acid (CPA),并将其用于构建半胱氨酸(Cys)检测的比率型荧光探针。研究表明,在水溶液中CPA以聚集态存在,分子的内旋转受限,非辐射衰减被抑制,发出橙色荧光;在DMSO溶液中,CPA分子具有良好的分散性,分子内基团的自由旋转和光致电子转移(PET)效应,导致非辐射通道开启,几乎不发出荧光;在50%~70%体积分数的DMSO水溶液中,由于溶液极性和氢键的影响,PET过程被禁阻,发出强烈的蓝色荧光。利用CPA这种在不同条件下荧光性质的改变,将其用于构建Cys荧光探针。在对Cys的检测过程中,CPA的最大发射波长从575 nm蓝移到了450 nm,并且伴随着比荧光强度对Cys浓度的线性增加,因此可以实现对Cys的比色法定性分析和比率法定量分析,检测限达到0.1 μM。 2、将N, N-二甲氨基苯胺与香豆素衍生物偶联,得到了结构简单的红光AIE分子8-[[[4-(dimethylamino)?phenyl]imino]methyl]-7-hydroxy-4-methyl-2H-1-benzopyran-2-one(CDPA)。其粉末和薄膜的荧光发射峰分别位于640 nm和645 nm处,光致发光量子效率分别达到了13.75%和26.33%,粉末态和薄膜态的色坐标分别为 (0.6527, 0.3472)和(0.6894, 0.3105),接近于国际标准红光材料色坐标(0.6700,0.3300)。该分子的制备过程具备原料易得,反应简单等优点。强推电子基团的引入还赋予该AIE分子显著的正溶致变色效应:随着溶剂极性的增大,荧光从正己烷中的黄绿光红移到乙醇中的红外光;以及TICT性能:在极性溶剂THF中,最大荧光发射峰在555 nm,随着非极性溶剂正己院的加入,发光逐渐蓝移至536 nm,强度明显增强。同时,该化合物还有良好的自组装性能,大的Stokes位移(245 nm),热稳定性好(热分解温度Td =298.5℃,相变温度Tg =243.4℃),热活性延迟荧光(TADF)性能以及溶液中颜色的可调节性,使其在橙光发光器件和红光生物探针等领域有着令人期待的应用前景。实验表明,CDPA的发光性质是基于激发态质子转移(ESIPT)过程和扭曲的分子内电荷转移(TICT)过程的共同作用引起的。利用CDPA制备的橙光OLEDs, 色坐标位于(0.51, 0.49),最大亮度和外量子效率分别达到1675 cd/m2和1.3%。 3、合成了三种新型的水杨醛席夫碱衍生物5-(diethylamino)-2-[[[4-(dimethylamino)phenyl]imino]methyl]phenol (C1),2-[[(4-(dimethylamino)phenyl)imino]methyl]-4-fluorophenol (C2)和5-(diethylamino)-2-[[(4-nitrophenyl)imino] methyl]phenol (C3),均表现出AIE性能和ESIPT过程,最大发射波长分别位于542 nm,572 nm和632 nm,相应的荧光量子效率(ФF)分别为27.8%,55.7%和68.1%。研究发现,三种化合物荧光性能的差异是由于推电子基(D)和拉电子基(A)的引入导致的。D–A作用能够引起分子构象和电子云分布的改变,起到调节荧光发射波长的作用。同时发现,三种AIE化合物在3.5~6.0的pH范围内随溶液pH值的改变发生变化,并且能够在EtOH/H2O溶液中对Zn2+具有特异响应性,因此可以用来构建pH和Zn2+荧光探针。 4、设计并合成了三种红光/近红外发射的邻羟基苯乙酮衍生物, 3-[4-(dimethylamino)phenyl]-1-(2-hydroxyphenyl)-2-propen-1-one (L1),1-(2-hydroxyphenyl)-3-[4-(1-pyrrolidinyl)phenyl]-2-propen-1-one (L2)和3-[4-(diphenylamino)phenyl]-1-(2-hydroxyphenyl)-2-propen-1-one (L3)。对比它们的荧光光谱发现,N, N –二甲氨基具有强烈的供电子能力,可以将其作为电子供体构建红光发射的荧光分子。然而,N, N-二甲氨基在构建荧光分子时,由于存在TICT效应,虽然可以引起发射波长的红移,但是也会带来荧光强度的降低,为了避免TICT过程的形成,我们分别引入五元氮杂环丁烷基和三苯胺基取代二甲氨基以减弱TICT的淬灭效应。结果表明,氮杂环丁烷可以有效提高荧光分子的发光性能并导致发射波长的显著红移。但是三苯胺基的引入导致分子构象趋于平面化,引起分子间π–π堆叠反而使荧光强度降低。因此,化合物L1, L2, L3固体的最大发射波长分别为685 nm,700 nm和617 nm,相应的荧光量子产率ФF分别为27.03%,49.48%和0.88%。分子L2具有良好的发光性能,可以作为荧光团应用于荧光探针等方面。在分子L2基础上发展起来的荧光探针probe 4 (2-[3-[4-(pyrrolidin-1-yl)phenyl]acryloyl]phenyl acrylate)表现出对Cys的专一识别性和良好的抗干扰性能,可以实现在红光/近红外波长范围对Cys特异性识别和定量检测。
英文题目 Synthesis and Property Investigation of Novel Organic Materials with “AIE+ESIPT” characteristics
英文主题词 Aggregation-Induced Emission, Aggregation-Caused Quenching,Excited State Intramolecular Proton Transfer,Fluorescent Probe, OELDs
英文摘要 Luminescent materials with aggregation-induced emission (AIE) property have received increasing attention in recent years and have been successfully applied in fluorescence probes or biosensors, bioimaging, OLEDs, optical waveguides, liquid crystal display, stimuli-responsive systems and so on for their efficient aggregate state emission and unique fluorescence “turn on” process. The emission wavelength and intensity of AIE-active compounds in the solid or aggregation state can be modulated by changing the composition of molecules, spatial conformation and accumulation patterns, which overcome the aggregation-caused quenching (ACQ) shortcoming of traditional fluorescent molecular. Herein, we have designed and synthesized a series of compounds with AIE performance based on coumarin and salicylaldehyde derivatives by readily available Schiff base condensation reactions. The central content of this dissertation is as follows: 1、A novel colorimetric and ratiometric fluorescence probe (4-[[(7-hydroxy-4-methyl-2-oxo-2H-1-benzopyran-8-yl)methylene]amino]benzoic acid, CPA) for the selective and sensitive monitoring of cysteine based on a coumarin Schiff-base platform was developed. This probe exhibited remarkable AIE characteristics with an exceptionally large blue shift (125 nm), which showed low emission in DMSO but strong aggregation-induced emission in water solution. An excellent linear relationship of fluorescence intensity ratio (F450/F575) (R2=0.9922) versus Cys concentration in the range of 0.1 μM ~13.0 μM was obtained. 2、An coumarin based red AIE fluorogen (8-[[[4-(dimethylamino)phenyl]imino]methyl]-7-hydroxy-4-methyl-2H-1-benzopyran-2-one, CDPA) was successfully synthesized by readily Schiff base reaction. Due to both the ESIPT and TICT processes, CDPA exhibits a strong red emission (λem=645 nm) with long emission lifetimes, an extraordinarily large Stokes shift of about 245 nm and high fluorescence quantum yield of 26.3% in solid state. The uniquely high quantum yield and rational tuning emission are demonstrated to originate from a combination effect of the molecular stacked design, ESIPT-active intramolecular H-bond, and TICT. With high red fluorescence quantum efficiency in solid states, good selfassembly performance, and significant TADF property, CDPA show potential application as remarkable emitter in the doped OLEDs, showing much high EL efficiencies. Additionally, the emitting device based on 3 has been successfully fabricated, achieving a maximum brightness of 1675 cd/m2 at 14 V (225 mA/cm2) with the CIE coordinates of (0.51, 0.49). Standing on this basis, not only is fine tuning the energetics of ESIPT of fundamental importance but also paves a new and feasible avenue route to yellow light generation. On the other hand, the finding is the first to show that coumarin derivatives possess the good photoelectric properties and can be used as luminescent materials in OLEDs. 3、Three new Schiff base derivatives 5-(diethylamino)-2-[[[4-(dimethylamino)phenyl]imino]methyl]phenol (C1),2-[[(4-(dimethylamino)phenyl) imino]methyl]- 4-fluorophenol (C2)和5-(diethylamino)-2-[[(4-nitrophenyl)imino] methyl]phenol (C3) possessing AIE and ESIPT characteristics with various fluorescence emissions from green to red and high fluorescence quantum yields in the aggregated state were synthesized using a facile and efficient method. Then, the effect of substituted group types and positions on the fluorescence of these novel compounds was investigated through fluorescence spectra analysis and theoretical calculations. And it was found that the different substituent groups in the salicylaldehyde moiety and in phenyl group produce the difference of optical properties, and these multiple-colour AIE molecules have a potential application of novel pH and Zn2+ chemosensors. 4、A series of red to near-infrared (NIR) emissive organic compound 3-[4-(dimethylamino)phenyl]-1-(2-hydroxyphenyl)-2-propen-1-one (L1),1-(2-hydroxy phenyl)-3-[4-(1-pyrrolidinyl)phenyl]-2-propen-1-one (L2) and 3-[4-(diphenylamino)phenyl]-1-(2-?hydroxyphenyl)-2-propen-1-one (L3) based on the 2’-hydroxyaceto- phenone derivatives were synthesized through a mild condensation reaction, which exhibit typical AIE properties, long fluorescence lifetime, the high quantum yield in an aggregated state. Comparison of their fluorescence properties clearly gives evidence that a subtle structure modification can arouse great property changes, which is instructive in designing new high-efficiency organic luminescent materials. In demonstration of the potential of this new fluorescence dye L2, the fluorescence probe 4 (2-[3-[4-(pyrrolidin-1-yl)phenyl]acryloyl]phenyl acrylate) that is capable of unique detecting Cys in water media is also constructed successfully.
学术讨论
主办单位时间地点报告人报告主题
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课题组组会 2015.9.28 新化工楼201 闫力强 热致变色材料
课题组组会 2014.12.20 新化工楼201 闫力强 A novel fluorescence chemosensor for Al3+
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学术会议
会议名称时间地点本人报告本人报告题目
Asian Advanced materials Congress(ASAMC2014) 2017.3.11-16 Singapore Aggregation induced emission (AIE) material and their applicaitons in fluorescent probe of Cys and luminescent device
2016年全国光谱技术与应用技术研讨会 2016.6.26-28 成都 基于AIE材料的荧光生物传感器
     
代表作
论文名称
A Simplified and Turn-on Fluorescence Chemosensor based on Coumarin Derivative for Detection of Alum
An aggregation-induced emission (AIE) ratiometric fluorescent cysteine probe with an exceptionally l
Synthesis and optical properties of aggregation-induced emission (AIE) molecules based on the ESIPT
A novel coumarin-based red fluorogen with AIE, self-assembly, and TADF properties
A simple salicylaldehyde-based fluorescent "turn-on" probe for selective detection of Zn2+ in water
A novel coumarin-based fluorescence chemosensor containing L-histidine for aluminium(III) ions in aq
 
答辩委员会组成信息
姓名职称导师类别工作单位是否主席备注
王明亮 正高 博导 东南大学
杨锦飞 正高 博导 南京师范大学
周钰明 正高 教授 博导 东南大学
王德才 正高 教授 博导 南京工业大学
练鸿振 正高 教授 博导 南京大学
王坤 正高 教授 博导 江苏大学
      
答辩秘书信息
姓名职称工作单位备注
薛忠俊 正高 高级工程师 东南大学