苝红620的高效绿色合成及其性能

以市售1,6,7,12-四氯-3,4,9,10-苝四甲酸二酐(TCPBA)为原料,合成了中间体N,N'-二(2,6-二异丙基)苯基-1,6,7,12-四氯-3,4,9,10-苝四甲酸二酰亚胺(BDIP-TCPBI)和产品N,N'-二(2,6-二异丙基)苯基-1,6,7,12-四苯氧基-3,4,9,10-苝四甲酸二酰亚胺(苝红620),其结构经IR、MS和NMR进行了确证。结果显示:反应中引入催化剂二水乙酸锌,使BDIP-TCPBI的合成时间缩短了一半,纯度(HPLC,下同)较文献纯度(68%)高出16%,其最佳工艺条件为:n(TCPBA)∶n(2,6-二异丙基苯胺)∶n(二水乙酸锌)∶n(丙酸)=1∶4∶0.2∶107,120℃反应12 h,产率为88%,纯度为84%;使用简便的洗涤代替柱色谱法使苝红620的纯度较文献纯度(82%)高出9%。苝红620的斯托克斯位移值为35 nm,循环伏安法获得苝红620的LUMO和HOMO轨道能级分别为–4.144和–4.470 e V,且具有较小的荧光自吸效应,是一种潜在的电子受体材料。     

新型红光材料——苝四羧酸二酰亚胺类化合物的合成及表征

以苝四羧酸酐为原料,成功合成了1,6,7,12-四溴-苝四酸酐、1,6,7,12-四溴-N,N '-二苯胺-苝四羧酸二酰亚胺和1,6,7,12-四对叔丁基苯氧基-N,N '-二苯胺-苝四羧酸二酰亚胺(PeryAnBp)3种化合物.经过柱分离得到较纯净的化合物PeryAnBp,并利用傅里叶红外光谱仪、元素分析仪、紫外可见光谱仪和核磁共振仪对其结构和性质做了表征.结果显示:PeryAnBp为一种红光材料,且其溶解性得到大大的改善.     

两种不对称苝酰亚胺小分子的合成及光伏应用研究

以3,4,9,10-苝四酸二酐为原料,通过在分子两端芳香环（bay位）分别连接2-甲氧基乙氧基和硝基,合成了两个不对称苝酰亚胺小分子N, N’-二(2-乙基己基)-1-(2-甲氧基乙氧基)-7-硝基-3,4,9,10-苝四羧酸二酰亚胺(Ⅲ)和N, N’-二(2-乙基己基)-1-(2-甲氧基乙氧基)-6,7-二硝基-3,4,9,10-苝四羧酸二酰亚胺(Ⅳ),利用1H NMR, 13C NMR和MS对其结构进行了表征。通过密度泛函理论计算优化了分子空间立体构象、扭曲结构和电子云分布;紫外-可见吸收光谱(UV-Vis)结果表明,与无取代基的苝酰亚胺相比,Ⅲ和Ⅳ的最大吸收峰红移至559 nm和572 nm。半峰宽变宽为104 nm和112 nm;经循环伏安(CV)测试估算分子Ⅲ和Ⅳ的HOMO、LUMO能级分别为−5.85 eV、−3.55 eV和−5.87 eV、−3.62 eV;在相对湿度为50%的在大气环境中,构建了有机太阳能电池器件,Ⅲ和Ⅳ分别与苯并二噻吩联噻吩并噻吩类聚合物（PTB7-Th）共混时器件性能分别提高到短路电流密度JSC= 3.6 mA/cm2,开路电压VOC=0.30V,填充因子FF= 0.40,光电转换效率PCE= 0.42%和JSC= 4.00 mA/cm2,VOC= 0.25 V,FF= 0.41,PCE= 0.40%。     

苝酰亚胺衍生物的合成及光谱性能研究

以3,4:9,10-苝四酸二酐为原料,合成了两种新型的苝酰亚胺衍生物:N-(1-己基庚基)-N'-苯基-3,4:9,10-苝四酸二酰亚胺和N-(1-己基庚基)-N'-苯基-1,7-二(4-叔丁基苯氧基)-3,4:9,10-苝四酸二酰亚胺,其结构经¹H NMR和MS表征。用紫外可见吸收光谱和荧光光谱研究了它们的光学性质,研究结果表明苝核海湾区供电子基团的引入,使得苝核的最大吸收波长发生了明显的红移,Stokes位移达到了29 nm。     

羟基-3,4,9,10-苝四羧酸二酰亚胺其合成方法及在氟含量测定中的应用

正本发明涉及1-羟基-3,4,9,10-苝四羧酸二酰亚胺、其合成方法及在氟含量测定中的应用。将1-NO2-3,4,9,10-苝四羧酸二酰亚胺与碱性盐混合溶于极性有机溶剂中40~80℃反应2~4小时,得到1-OH-3,4,9,10-苝四羧酸二酰亚胺。1-OH-3,4,9,10-苝四羧酸二酰亚胺对环境中     

吸电子基对苝酰亚胺微纳米结构传感性能的影响

在苝四酸酐的苝湾(1,7位或1,6,7,12位)位置引入—Cl或—CN,分别制备了两种苝酰亚胺衍生物N,N-双(七氟丁基)-1,6,7,12-四氯-3,4:9,10-苝二酰亚胺(PTCDI-ClF7)和N,N-双(七氟丁基)-1,7-二氰基-3,4:9,10-苝二酰亚胺(PTCDI-CNF7),探索了其在氯仿/甲醇混合溶液中的超分子自组装并测定其微/纳米结构的气敏传感性能。研究显示,两种化合物在苯肼氛围中的灵敏度变化不同,PTCDI-ClF7气敏传感器电阻下降比PTCDI-CNF7高出近2个数量级,其原因是两者占据的最低未占分子轨道(LUMO)能级值相差较大。结果表明:湾位吸电子取代基的不同对苝酰亚胺衍生物微/纳米结构的气敏传感性能影响显著。     

含叔胺基团苝酰亚胺的合成及其自组装性能

利用苝酐为原料,合成了两种不同碳链长度叔胺基取代的苝酰亚胺分子N,N-二(N,N-二甲基乙二胺基)-1,6,7,12-四(4-叔丁基苯氧基)-3,4,9,10-苝四甲酸酰亚胺(MDI-PBI)和N,N-二(3-二甲胺基丙胺基)-1,6,7,12-四(4-叔丁基苯氧基)-3,4,9,10-苝四甲酸酰亚胺(MPI-PBI),两分子分别在两种两相溶剂体系中进行快速溶剂扩散自组装。利用SEM、UV-Vis、偏光干涉和XRD对聚集体形貌结构、光物理性能和内部分子排列情况进行了表征。结果表明,两分子在甲醇中的溶解度(S)比在正己烷中大,且S(MPI-PBI)S(MDI-PBI)。MDI-PBI和MPI-PBI在两种自组装体系中均为J型聚集,疏溶剂化作用较强时,分子形成聚集程度更高、更稳定的纳米带或纳米线;疏溶剂化作用较弱时,形成球状结构。π–π堆积作用为MDI-PBI聚集体长轴方向生长的作用力,疏溶剂作用为短轴方向生长的作用力,叔胺取代基碳链更长的MPI-PBI则刚好相反。V(甲醇)∶V(THF)=5∶1情况下MDI-PBI形成的纳米带内部分子之间π–π堆积的距离为0.37 nm,并根据此结果得到了其内部分子的堆积模型。     

两种不对称苝酰亚胺小分子的合成及光伏应用

以3,4,9,10-苝四酸二酐为原料,通过在分子两端芳香环(bay位)分别连接2-甲氧基乙氧基和硝基,合成了两个不对称苝酰亚胺小分子N,N'-二(2-乙基己基)-1-(2-甲氧基乙氧基)-7-硝基-3,4,9,10-苝四羧酸二酰亚胺(Ⅲ)和N,N'-二(2-乙基己基)-1-(2-甲氧基乙氧基)-6,7-二硝基-3,4,9,10-苝四羧酸二酰亚胺(Ⅳ)。利用1HNMR,13CNMR和MS对其结构进行了表征。通过密度泛函理论计算优化了分子空间立体构象、扭曲结构和电子云分布;紫外-可见吸收光谱结果表明,Ⅲ和Ⅳ的最大吸收峰红移至559和572 nm,半峰宽变宽,为104和112 nm;经循环伏安(CV)测试估算,分子Ⅲ和Ⅳ的HOMO、LUMO能级分别为-5.85、-3.55 e V和-5.87、-3.62 e V;在相对湿度为50%的大气环境中,Ⅲ和Ⅳ分别与窄带隙聚合物(PTB7-Th)共混构建了有机太阳能电池器件,Ⅲ与PTB7-Th共混时对应的短路电流密度Jsc=3.6 m A/cm2,开路电压Voc=0.30 V,填充因子FF=0.40,光电转换效率η=0.42%;Ⅳ与PTB7-Th共混时对应的Jsc=4.00 m A/cm2,Voc=0.25 V,FF=0.41,η=0.40%。     

单边苯基苝酰亚胺的合成工艺研究

研究了以3,4,9,10-苝四羧酸二酐为原料,经过水解,酸酐化,苯胺酰亚胺化,乙酸铵条件下酰亚胺化,最终制备得到不对称的N-苯基苝酰亚胺分子。通过红外光谱分析表征了结构。     

萘二甲酸酐生产工艺的开发

苊经液相或气相氧化可制取萘二甲酸酐(NAA),主要用作苝系颜料的原料。大部分苝系颜料为N,N-3,4,9,10-苝四羧酸亚胺,具有代表性的生产方法是以苊氧化反应后所得的萘二甲酸酐为基本原料,制造苝四羧酸酐,并使1级胺与其发生反应(图1)。     

苝系颜料及商品化技术

该文讨论了苝系颜料的品种、合成，结构特性、同质异晶现象、晶型及其应用性能等；介绍了苝系颜料的商品化技术，诸如：隐色体氧化、酸处理、溶剂处理、研磨技术、颜料衍生物处理、不同添加剂改性及共缩合技术等。     

High-Efficiency Sorbent for Dyes Based on Cellulose Resin Crosslinked with Perylene Tetracarboxylic Diimides

The novel cellulose resin crosslinked with perylene tetracarboxylic diimides 3 was synthesized and its structure was characterized by elemental analysis, Fourier transform infrared (FTIR) spectroscopy, and scanning electronmicroscopy (SEM), etc. Dyes adsorption experiments of polymer 3 suggested that it exhibited excellent adsorption capacities for tested four cationic and anionic dyes [Orange G sodium salt (OG), Brilliant ponceau 5R (BP), Methylene blue (MB), and Crystal violet (CV)]. The adsorption capacities for OG, BP, MB, CV were as high as 1.04, 1.21, 1.14, and 0.96 mmol/g, respectively. The adsorption processes obeyed the pseudo second-order model and followed the Langmuir isotherm equation. The adsorption processes were exothermic and spontaneous. The pH = 2 ? 12 made slight influences on adsorption capacities of polymer 3 for dyes. It was supposed that the adsorption mechanism was not only the electrostatic forces and hydrogen bond but also the π-π stacking interaction playing an important role in the adsorption processes.     

Highly Soluble Monoamino-Substituted Perylene Tetracarboxylic Dianhydrides: Synthesis,Optical and Electrochemical Properties

Three dialkylamino-substituted perylene tetracarboxylic dianhydrides with different n-alkyl chain lengths (n = 6, 12 or 18), 1a–1c, were synthesized under mild conditions in high yields and were characterized by ¹H NMR, ¹³C NMR and high resolution mass spectroscopy. Their optical and electrochemical properties were measured using UV-Vis and emission spectroscopic techniques, as well as cyclic voltammetry (CV). This is the first time that the structures and the properties of monoamino-substituted perylene tetracarboxylic dianhydrides have been reported. These molecules show a deep green color in both solution and the solid state and are soluble in most organic solvents. They all show a unique charge transfer emission in the near-infrared region, and the associated peaks exhibit solvatochromism. The dipole moments of the compounds have been estimated using the Lippert-Mataga equation, and upon excitation, they show slightly larger dipole moment changes than those of corresponding perylene diimides, 2a–2c. Additionally, Compounds 1a–1c undergo two quasi-reversible one-electron oxidations and two quasi-reversible one-electron reductions in dichloromethane at modest potentials. Complementary density functional theory calculations performed on these chromophores are reported in order to gain more insight into their molecular structures and optical properties.     

苝醌类化合物总量的测定

用分光光度法测定了竹红菌、竹黄和菌寄生菌培养物中艹北 醌类化合物的总量 ;同时研究了以无水乙醇、丙酮和氯仿为溶剂提取 艹北 醌类化合物的相对效率 ,结果发现以丙酮为溶剂最合适。     

Structural and Optical Properties of New Naphthalene and Perylene Imide Imidazoles

ABSTRACT

New unsymmetrically substituted naphthalene and perylene imide imidazoles, N-(2-ethylhexyl)-naphthalene-3,4-(4,5-dicyano-1,2-benzimidazole)-9,10-dicarboxyimide and N-(1-heptyloctyl)-perilene-3,4-(4,5-dicyano-1,2-benzimid-azole)-9,10-dicarboxyimide, were synthesized via condensation reactions of diaminophthalonitrile and aromatic monoimide monoanhydride derivatives. Their structural analyses have been conducted by using general spectroscopic methods including FT-IR, ¹H- and ¹³C-NMR, mass and elemental analysis. The molecular structure of naphthalene derivative was also determined by single crystal x-ray diffraction. Electronic absorption and emission properties were investigated on comparison. For studied compounds, both DFT and TDDFT calculations were carried out with the 6-311G(d,p) basis set, taking into account solvation effects by means of polarizable continuum model as implemented in the Gaussian 09 package.     

Optical study of perylene dye doped poly(methyl methacrylate) as fluorescent solar collector

The optical absorption of poly(methyl methacrylate) (PMMA), doped with perylene dye, prepared by both thermal polymerization and casting methods, has been measured before and after exposure to filtered or unfiltered light using xenon arc lamp or day light. The optical band gap of thermally polymerized PMMA was reduced by doping with perylene dye or exposure to UV radiation. Study of DSC and FTIR measurements confirmed that the samples prepared by thermal polymerization are more stable than solvent‐cast samples. © 2002 Society of Chemical Industry     

拉伸PVA膜法中膜的拉伸与分子取向的关系

通过对苝的二向色性电子光谱的解析,讨论了拉伸高分子膜法光谱实验中取向轴面及分子平面的关系     

逐层组装多层膜对苝的固相萃取性能研究

利用聚电解质逐层自组装技术在氨基硅胶表面构筑聚(乙烯-alt-马来酸)的苯乙胺衍生物(PEMAPEA)/聚烯丙基胺盐酸盐(PAH)多层膜,制备性能稳定的新型固相萃取吸附材料。利用HPLC-UV/Vis检测,研究其对水体中苝的萃取性能,考察柱填料量、样品量、上样流速、洗脱溶剂等对多层膜萃取性能的影响。结果表明:含150 mg固相萃取填料的3 mL萃取小柱,以10 mL·min-1的流速萃取200 mL苝的水溶液,用丙酮作洗脱剂,萃取回收率达到90%以上。