苝四羧酸二酰亚胺衍生物的合成及其性能研究

以苝四羧酸二酐为原料,设计并合成了3个苝四羧酸二酰亚胺类化合物[1,7-二溴-3,4,9,10-苝四酸酐(1), N,N′-二(十二烷基)-1,7-二溴-3,4,9,10-苝四羧酸二酰亚胺(2)和N,N′-二(十二烷基)-1,7-二对叔丁基苯氧基-3,4,9,10-苝四羧酸二酰亚胺(3)],其结构经1H NMR和MS表征.用循环伏安法和热分析法研究了2和3的电化学性质和热学性质.结果表明:2和3的氧化电位分别为931.6 mV, 170.1 mV,还原电位分别为-1 028 mV, -1 941 mV;2和3具有高的分解温度(>300 ℃),有良好的热稳定性.     

可溶性苝四羧酸二酰亚胺发光材料的合成及表征

以苝四酸酐为原料合成了1,7-二溴-3,4,9,10-苝四酸酐(PeryBr₂)、N,N′-二(十二烷基)-1,7-二溴-3,4,9,10-苝四羧酸二酰亚胺(DD-PeryBr₂)和N,N′-二(十二烷基)-1,7-二对叔丁基苯氧基-3,4,9,10-苝四羧酸二酰亚胺(DD-PeryBp₂) 3种苝四羧酸二酰亚胺类化合物,并对其结构和性能利用紫外-可见吸收光谱、傅立叶红外光谱、核磁共振、质谱、热分析和荧光光谱测试技术进行了表征和测试。 结果表明,DD-PeryBp₂能很好的溶于甲苯、氯仿、四氢呋喃等常用有机溶剂。 紫外可见最大吸收波长和荧光最大发射波长分别为548和576 nm。 DD-PeryBp₂具有很好的热稳定性,质量损失5%时的温度为433 ℃。     

N,N’-二(2-吡啶基)-1,6,7,12-四(4-叔丁基苯氧基)-3,4:9,10-苝酰亚胺的合成、表征及性能研究

优化了N,N’-二(2-吡啶基)-1,6,7,12-四(4-叔丁基苯氧基)-3,4:9,10-苝酰亚胺的合成方法, 得到一种简单有效的在苝酰亚胺的酰胺和bay位置同时取代的方法. 对其结构进行了表征, 研究了其溶液态和薄膜态的光学性质和电化学性质. 并且对其能级结构和电荷分布进行了分子模拟.     

一种新型苝酰亚胺的合成及其与C60之间的电荷转移作用

设计和合成了一种新型苝酰亚胺电子受体—N,N ′-二嘧啶基苝四羧基二酰亚胺(DMP), 利用傅里叶红外光谱和元素分析表征了DMP的分子结构. 通过与N,N ′-二苯基-3,4,9,10-苝四羧基二酰亚胺(DPP)的循环伏安实验的对比, 证明了嘧啶基的引入降低了分子的LUMO能级. 研究了DMP与C₆₀层-层蒸镀(layer-by-layer evaporation)薄膜的荧光变化, 确认其界面处发生了由于能级位置差异导致的电荷转移.     

取代基对苝酰亚胺衍生物气敏传感性能的影响

制备了两类酰胺位置含有吸电子基团的苝酰亚胺衍生物N,N′-双(三氟乙基)-1,7-二溴-3,4,9,10-苝二酰亚胺(PTCDI-3F)和N,N′-双(七氟丁基)-1,7-二溴-3,4,9,10-苝二酰亚胺(PTCDI-7F),并测定了其气敏传感性能.结果表明,两类苝酰亚胺衍生物在水合肼气氛中(10ppm)的灵敏度变化值基本相同、电阻均降低约4个数量级.其原因在于两者具有相同的最低空轨道能级.这表明酰胺位取代基对苝酰亚胺衍生物气敏传感性能的影响较小.     

具有好的溶解性和高的热稳定性的富勒烯-苝化合物的合成

在氩气保护下，利用N-(正丁基)-N’(4-甲酰基苯氧戊基)-1．6，7，12-四-(4-叔丁基苯氧基)-3，4，9，10-苝酰亚胺和N-甲基甘氨酸产生的亚胺叶立德与富勒烯反应，合成了含富勒烯的苝化合物，用NMR、FT—IR、UV-Vis及TGA等方法对其结构和性能进行了表征和测试。研究结果表明此类化合物具有好的溶解性和高的热稳定性。     

微波辐射合成N,N-二苯基-3,4,9,10-苝二酰亚胺

以3,4,9,10-苝四酸酐为原料,无水醋酸锌为催化剂,与苯胺利用微波辐射,合成N,N-二苯基-3,4,9,10-苝二酰亚胺.研究结果表明,在微波辐射下,无水醋酸锌对该反应有较好的催化活性,N,N-二苯基-3,4,9,10-苝二酰亚胺的产率可达60.02%.实验确定了该反应的最终优化条件为:无水醋酸锌的用量为0.5g,微波辐射功率为900 W,辐射时间为50min,反应温度为150℃.     

一种新型π-共轭聚合物的合成研究:苝酰亚胺的Stille偶联

苝酰亚胺衍生物是国内外近年来广泛研究的π-共轭低聚物,由于其独特的半导体传导性、高热稳定性、较高的电子亲和性和卓越的传输性能在众多领域具有潜在的应用价值。通过对其海湾位置进行结构修饰,可进一步改善其物理化学性能。本文利用苝酰亚胺的Stille偶联反应合成了一种新型的聚(N,N’-二(2-乙基己基)苝-3,4,9,10-四甲酸二酰亚胺),它具有近似石墨烯带状的规整结构和宽广的光谱吸收,成功将苝核四溴代的海湾位置用四丁基锡取代,对产品分别进行了IR、NMR和GPC-MALLS表征,并对这种具有特殊π-共轭结构的新型聚合物的光化学性能进行了研究。     

N,N＇-二（2-吡啶基）-1,6,7,12-四（4-叔丁基苯氧基）-3,4：9,10-苝酰亚胺的合成、表征及性能研究

优化了N,N＇-二（2-吡啶基）-1,6,7,12-四（4-叔丁基苯氧基）-3,4：9,10-苝酰亚胺的合成方法,得到一种简单有效的在苝酰亚胺的酰胺和bay位置同时取代的方法.对其结构进行了表征,研究了其溶液态和薄膜态的光学性质和电化学性质.并且对其能级结构和电荷分布进行了分子模拟。     

不同pH环境中离子化水溶性染料分子的荧光性质

本文以3,4,9,10-苝四羧酸酐为原料合成了3,4,9,10-苝四羧酸和N,N′-二((3-二甲氨基)丙基)-3,4,9,10-苝二酰亚胺,这两个苝系衍生物在水溶液中的溶解度和荧光效率并不高,但是在不同的pH值条件下,两个衍生物形成了水溶性较强的PTCA阴离子和PMI阳离子,并且具有不同的荧光性质。实验结果显示:PTCA在pH 10.0的碱性环境中显示出较强的蓝色荧光,PMI在pH 5.0的弱酸性环境中显示出较强的黄色荧光,并且根据测试的荧光光谱推测了两种具有相同发色团、相似结构的衍生物在不同pH环境中可能存在分子或离子的堆积模式及发光模式。本文还探讨了PTCA阳离子在pH 6.0缓冲溶液中,作为离子型荧光探针对部分金属离子的识别。     

可溶性的含羧基苝酰亚胺类化合物的合成及其光谱性质研究

本文主要以酐(1)为起始物,通过在环母体结构的1、6、7、12位上引入苯氧基和对甲基苯氧基合成了另外两种酐化合物(2a和2b);所得到的酐化合物与6-氨基已酸进行反应,合成了3种可溶性的含有羧基的酰亚胺化合物(3a、3b和3c),使用红外、紫外、荧光、¹H-NMR,元素分析对所合成的化合物进行了表征.经研究发现,环母体结构的1、6、7、12位上苯氧基和对甲基苯氧基的引入,能使得所合成的含羧基酰亚胺类化合物的最大吸收波长分别红移了44.1 nm和50.1 nm;Stokes位移变大,分别为34.1 nm和30.0 nm;而荧光量子产率有所降低但下降趋势不明显.     

Self-assembled helical nanostructures from an asymmetrical perylene diimide

An asymmetrical perylene diimide 3, N-（4-methoxyphenyl）-N＇-（4-nitrophenyl）-perylene-3,4,9,10-tetracarboxylic diimide, was synthesized, and its self-assembly and dissociation behaviors in chloroform was studied in detail by UV-vis and fluorescence spectroscopies. The resulting unique helical nanostructures from 3 were proposed to be self-assembled via the cooperative actions of π-π stacking, steric hindrance and electrophile-nucleophile type pairing.     

二萘嵌苯二酰亚胺衍生物的半导体性质

应用密度泛函理论研究了四种二萘嵌苯二酰亚胺(PDI)(N,N'-二萘嵌苯-3,4,9,10-四羧酸二酰亚胺(1), N,N'-二(3-氯苯甲基)二萘嵌苯-3,4,9,10-四羧酸二酰亚胺(2), N,N'-二(3-氟苯甲基)二萘嵌苯-3,4,9,10-四羧酸二酰亚胺(3)和N,N'-二(3,3-二氟苯甲基)二萘嵌苯-3,4,9,10-四羧酸二酰亚胺(4))半导体材料的最高占据轨道和最低未占据轨道能量、离子化能和电子亲和能以及在电荷传导过程中的重组能. 与化合物2-4的最高占据轨道和最低未占据轨道能量变化相同, 在PDI分子外围引入氯苯甲基或氟苯甲基后导致化合物2-4的绝热电子亲和能有不同程度的增加. 应用Marcus电子传导理论, 计算了这四种半导体材料应用于有机场效应晶体管在电子传递过程中的电子耦合和迁移率. 计算结果表明:这四种化合物相对于金属金电极而言具有较小的电子注入势垒, 是优良的n型半导体材料. 计算的这四种半导体材料的电子传输迁移率分别为5.39, 0.59, 0.023和0.17 cm2·V-1·s-1. 通过研究化合物分子在还原过程中几何结构变化和在化合物3晶体中不同类型的电子传递路径, 合理地解释了化合物1-4在有机场效应晶体管电荷迁移过程中具有较高的电子迁移率.     

Effect of side-chain substituents on self-assembly of perylene diimide molecules: morphology control

Effect of side-chain substitutions on the morphology of self-assembly of perylene diimide molecules has been studied with two derivatives modified with distinctly different side-chains, N,N'-di(dodecyl)-perylene-3,4,9,10-tetracarboxylic diimide (DD-PTCDI) and N,N'-di(nonyldecyl)-perylene-3,4,9,10-tetracarboxylic diimide (ND-PTCDI). Due to the different side-chain interference, the self-assembly of the two molecules results in totally different morphologies in aggregate: one-dimensional (1D) nanobelt vs zero-dimensional (0D) nanoparticle. The size, shape, and topography of the self-assemblies were extensively characterized by a variety of microscopies including SEM, TEM, AFM, and fluorescence microscopy. The distinct morphologies of self-assembly have been obtained from both the solution-based processing and surface-supported solvent-vapor annealing. The nanobelts of DD-PTCDI fabricated in solution can feasibly be transferred to both polar (e.g., glass) and nonpolar (e.g., carbon) surfaces, implying the high stability of the molecular assembly (due to the strong pi-pi stacking). The side-chain-dependent molecular interaction was comparatively investigated using various spectrometries including UV-vis absorption, fluorescence, X-ray diffraction, and differential scanning calorimetry. Compared to the emission of ND-PTCDI aggregate, the emission of DD-PTCDI aggregate was significantly red-shifted (ca. 30 nm) and the emission quantum yield decreased about three times, primarily due to the more favorable molecular stacking for DD-PTCID. Moreover, the aggregate of DD-PTCDI shows a pronounced absorption band at the longer wavelength, whereas the absorption of ND-PTCDI aggregate is not significant in the same wavelength region. These optical spectral observations are reminiscent of the previous theoretical investigation on the side-chain-modulated electronic properties of PTCDI assembly.     

Synthesis of a novel perylene diimide derivative and its charge transfer interaction with C60

A novel organic electron acceptor, N,N′-dipyrimidinyl-3,4,9,10-perylene-tetracarboxylic diimide (DMP), was designed and synthesized. The molecular structure was characterized by FTIR spectrum and elemental analysis. By cyclic voltammetry measurements, DMP was found to possess a lower LUMO energy level than N,N′-diphenyl-3,4,9,10-perylene-tetracarboxylic diimide due to the stronger electron-withdrawing pyrimidinyl group than the phenyl group. Fluorescence quenching is observed in a dual-layer film consisting of a DMP layer and a C₆₀ layer and was attributed to the charge transfer at the interface due to the energy level offset between DMP and C₆₀.     

水溶性苝系衍生物荧光探针的合成及对金属离子的识别

用苝四酸酐为反应物,在酸酐位置上引入天冬氨酸,合成了水溶性的含4个羧基的荧光苝二酰亚胺衍生物:N,N'-二天冬氨酸铵盐-3,4,91,0-苝四羧酸二酰亚胺(PTCDA).在水溶液中与Fe3+、Al3+、Pb2+和Cu2+等金属离子反应,吸收光谱发生红移,荧光淬灭.当加入等量Hg2+、Zn2+、Ni2+、Co2+、Mn2+和Mg2+等金属离子后不干扰荧光反应,有选择性好、灵敏度高等特点.并探讨了衍生物的荧光反应机理,表明有好的应用价值和广阔发展前景。     

Non-classical control of solid-state aggregation-induced enhanced circularly polarized luminescence in chiral perylene diimides

Organic fluorescent molecules are gaining importance because of their potential applications in many devices. Optically active N,N′-bis((1R)-1-naphthylethyl)perylene-3,4,9,10-tetracarboxylic diimide [(R,R)-1-BNP] and N,N′-bis((1R)-2-naphthylethyl)perylene-3,4,9,10-tetracarboxylic diimide [(R,R)-2-BNP] and their antipode, [(S,S)-1-BNP and (S,S)-2-BNP], emit aggregation-induced enhanced (AIEnh) circularly polarized luminescence (CPL) on both a solid organic polymer film (poly(methyl methacrylate)) and solid inorganic KBr pellet. An opposite chirality is essential for generating CPL of inverted sign. However, a pair of enantiomeric organic molecules may not always be easy to prepare. Interestingly, the chiral perylene fluorophores synthesized in this study can emit both positive and negative AIEnh-CPL in the solid state, depending on their position on the naphthylene groups. In addition, no CPL was observed in these compounds from their dilute solutions.     

Synthesis of highly fluorescent and water soluble perylene bisimide

Designed and synthesized a new highly water soluble N,N¹-bis（2-（（5-（（dimethylamino）methyl）furan-2-yl）methylthio）ethyl）-perylene -3,4,9,10-tetracarboxylic diimide from 2-（（5-（（dimethylamino）methyl）furan-2-yl）methylthio）ethanamine and perylene-3,4,9,10- tetracarboxylic dianhydride.The compound was characterized by ¹H,¹³C,2D NMR,mass and IR techniques.The compound is highly fluorescent with good solubility in water and other polar solvents.