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The macro conjugated molecule fluorene derivative has 2, 3, 6, 7-tetraamino-9, 9'-dialkyl fluorene as a raw material which is added to an organic solvent respectively together with phenanthrenequinone, acenaphthene quinone or bis-carbonyl pyrene derivatives and strong base; under the protection of inert gas, reflux reaction is carried out to the materials, so as to prepare a series of trapezoidal conjugated molecules containing fluorine structures.

本发明涉及一类含大共轭分子的芴衍生物及其制备方法,大共轭分子芴衍生物是将原料2,3,6,7-四氨基-9,9'-二烷基芴,分别与菲醌、苊醌或二羰基芘的衍生物以及强碱加入到有机溶剂中,在惰性气体的保护下,回流反应制得一系列含有芴结构的梯形共轭分子。

The kinds of compounds with AIE, AIEE and CIEE are summarized, mainly including siloles, substituted ethenes (mainly including fulvene and DPDSB style), CN-MBE, pyran, biphenyl compounds and polymers.

侧重总结了silole型、取代乙烯型(主要包括亚甲基环戊二烯型和DPDSB型)、腈取代二苯乙烯型、吡喃型、联苯型等小分子化合物和少数高分子的结构与AIE性质之间的关系,以及为解释AIE现象所提出的限制分子内的转动、避免非辐射去活、构象扭曲避免形成excimer、J-聚集态以及形成分子间的C-H/π键等理论。

Anethole accounted for 82.65% of the whole oil. Selective isolation of anethole form the volatile oil was carried out using an inclusion crystalline method with 1,1,6,6- tetraphenylhexa- 2,4-diyne-1,6-diol inclusion complex with anethole . The crystal structure of the inclusion complex was determined by IR, 1^H NMR and single crystal XRD techniques.

采用包结结晶方法对小茴香挥发油中的对-丙烯基茴醚进行了选择性分离,以1,1,6,6-四苯基-2,4-已二炔-1,6-二醇作为主体分子,小茴香挥发油中的对-丙烯基茴香醚作为客体分子,D.D选择性地与之形成超分子包结物晶体。

The main contents are:(1) The polarized laser Raman spectra of acetone, methyl alcohol, alcohol, ethylene glycol, formamide, acetonitrile, acetic acid, Chloroform, Methylene chloride, and Bromoform are measured in the experiment.(2) The depolarization ratio of Raman shift in the measured spectrum are

主要的结果有:得到了丙酮分子9条喇曼谱线、甲醇分子5条喇曼谱线、乙醇分子9条喇曼谱线、乙二醇分子7条喇曼谱线、甲酰胺分子8条喇曼谱线、乙腈分子8条喇曼谱线、乙酸分子8条喇曼谱线

Each of them exhibited sensitive reduction responses of nitryls. It was found that the reduction peak of nitryl of the position 4-nitrate group of 2,4-dinitrophenol showed great difference from that of the position 5-nitrate group of 2,5-dinitrophenol. The difference between the two reduction potentials was as large as 180 mV.

在pH=5.0、0.1mol/LNaAc-HAc缓冲体系中,2,4-二硝基苯酚和2,5-二硝基苯酚在碳纳米管修饰电极上出现灵敏的硝基还原峰,其中2,4-二硝基苯酚分子中四位硝基的还原峰和2,5-二硝基苯酚分子中五位硝基的还原峰显示出明显差异,二者峰电位差达180mV。

The UV and IR spectroscopic studies of the monomer films showed that the photoreaction ratio of monomer (about 50%) was higher than the corresponding photosensitive polymer (about 10%, PVCi). The polarized IR spectra proved that obvious anisotropic absorption was displayed in the irradiated photosensitive film. With polarizing microscopy method, we found that these kinds of photoalignment films exhibited good alignment ability, and the stability of the photoalignment film could reach about 100℃. 2 A photosensitive self-assembled monolayer was fabricated that contained photo-cycloadditable groups, such as, coumarin and cinnamate. The reaction process were detected by contact angle method because the IR absorption of monolayer was very weak. The photosensitive self-assembled monolayer promote uniform alignment of nematic liquid crystals by LPUV, and it thermal stability could reach about 130℃. 3 A cationic bolaform amphiphiles was synthesized that had two photosensitive double bonds, and can be polymerized by ultraviolet. A layer-by-layer self-assembled deposition film was prepared in aqueous solution by using this material and poly (sodium 4-styrenesulfonate). The UV-Vis. spectra proved that the multilayers film was uniform and layer-by-layer. When LPUV irradiated the film, the photopolymerizable double bond underwent [2+2] cycloaddition, and the production of the reaction distributed along the polarized direction of incident LPUV. Polarized UV-Vis. spectra indicated that the irradiated self-assembled multiplayer film was anisotropic, and the dichromic ration is about 0.09, it is higher than the spin-coating method of photosensitive polymer or monomer. We used this anisotropic film as alignment layer of nematic liquid crystals, and obtained a uniform and stability alignment result, the static contrast ratio is about 100, which is very close to application of liquid crystal device. This thesis is an instance that the photochemical material was used in the physics region of liquid crystals, the route that was from photosensitive monomer, self-assembled monolayer film to self-assembled multiplayer film was undergone, by this logical research method photoailgnment of liquid crystal was extended and consummated.

围绕上述思路开展了如下工作:1合成了三种可进行光二聚反应的光敏小分子单体,LPUV 辐照制作了光控取向膜;用紫外-可见光谱法和红外光谱法分析了薄膜中的光化学反应,发现小分子的光反应程度可达到50%以上,至少比光敏高分子高出5倍;薄膜的偏振红外光谱证实,经过LPUV 辐照后薄膜出现了明显的各向异性;将小分子光控取向膜制成液晶器件,在偏光显微镜下观察看到均匀一致的液晶取向;并且热稳定性达到100℃左右,接近实用化要求。2制备了含肉桂酸、香豆素基团的自组装单层膜;采用接触角的方法监测自组装反应的动力学过程;紫外-可见光谱证实了自组装单层膜在石英基板表面形成;自组装单层膜经LPUV 辐照后能诱导液晶均匀取向,而且热稳定性可达130℃,热稳定性进一步提高。3合成了含有光敏双键的双季铵盐,在水溶液状态下将它和聚乙烯基苯磺酸钠沉积生成layer-by-layer 自组装多层膜,紫外-可见光谱证实这是一个逐层均匀的沉积;在LPUV 照射下,自组装膜中的光敏双键按照偏振方向发生[2+2]环加成反应,形成取向膜,用二向色性值评价的分子取向度高于高分子及小分子光控取向膜的水平;实验证明用自组装多层膜制成的液晶器件亮暗态均匀,静态对比度约为100,达到实用化器件的水平。

In chapter four, the preperation of ytterbium diiodide was examined. The reductive cleavage of Se-Se bond and S-S bond induced by ytterbium diiodide was investigated. The reaction of diselenides and disulfides with allylic bromide promoted by ytterbium diiodide was also examined. The intermolecular Barbier-type reaction induced by ytterbium diiodide was studied. In the last section of this chapter, the intermolecular reductive coupling of nitriles with azides induced by samarium diiodide was investigated.

第四章,研究了二碘化镱的制备方法,以及二碘化镱作为一种优良的单电子转移试剂在有机合成中的应用:二硒醚的Se--Se键和二硫醚S-S键的还原断裂,及其在合成烯丙基硒醚,硒代酯和烯丙基硫醚,硫代酯中的应用,实验结果表明二碘化镱也能促进分子间的Barbier反应,而文献认为二碘化镱不能促进分子间的Barbier反应;最后研究了二碘化钐促进的叠氮化合物与腈的交叉还原偶联反应,一步高收率地制备脒的方法。

Collisional induced dissociation technique is applied to characterize cucurbituril supramolecule structures complexed with 1,4-diaminobutane, phenylenediamine and lysine.

运用碰撞激发解析技术确定了葫芦脲[6]与1,4-丁二胺,二甲基苯以及赖氨酸分子形成轮轴结构的超分子复合物,即线性分子穿入葫芦脲[6]的空腔内形成的稳定超分子复合物。

objective: to prepare the molecularly imprinted composite membranes with propofol as template.methods: with the ultraviolet light and initiator, template molecular propofol, functional monomer methacrylate and crosslinking agent ethylenegly-coldimethacrylate formed molecularly imprinted composite membrane through polymerization on the surface of polyvinyli-dene fluoride microporous membrane.inspection of the combination of template molecule and functional monomer, characterization of the membrane surface morphology with scanning electron microscopy.results: the morphology of composite membranes was well.propofol bonded to methylacrylic acid with hydrogen bond.conclusion: the method of ultraviolet light-struck is feasible for preparation of molecularly imprinted composite membranes with propofol as template.

目的:制备异丙酚分子印迹复合膜。方法:在紫外光照和引发剂的作用下,模板分子异丙酚、功能单体甲基丙烯酸和交联剂乙二醇二甲基丙烯酸酯在聚偏氟乙烯微孔滤膜表面聚合形成分子印迹复合膜,考察模板分子和功能单体的结合特性,用扫描电镜表征膜的表面形态。结果:复合膜形态良好,异丙酚和甲基丙烯酸以氢键的方式缔合。结论:用紫外光照射法可以制得异丙酚分子印迹复合膜。

Therefore, the EL spectra of (Znq_2)_4 is wider than that of Znq_2. 4._2 was synthesized. The analysis of molecular spatial structure and the characterization of material performance of_2 and Liq showed that two Liq molecules and two Naq molecules were connected by Na-O-Na bond bridges to form_2. Compared with Liq,_2 exhibits stronger rigidity in planar molecular structure, larger steric hindrance and intermolecular distance, and much smaller molecular polarity, thus resulting in much longer fluorescence lifetime, much higher fluorescence quantum efficiency, wider energy bandgap and better film formability. When used as light-emitting layer in OLED,_2 shows lower formation probability of excited dimmer and exciplex formation than Liq, thus emits bluer light with higher current efficiency than Liq. When_2 ultrathin film is used as electron injection layer in OLED, it exhibits higher current density, higher luminance, lower turn-on voltage and higher current efficiency than Liq ultrathin film for the existence of sodium ions in_2 ultrathin film. 5. The summarization the relationship between molecular spatial structure and material performance of Alq_3,(Znq_2) and Liq, lead the conclusion that the molecular spatial structure of Mq_n affects its material performance in such aspects as the rigidity of planar molecular structure, intermolecular interaction, molecule stacking mode and intermolecular distance.

制备了_2,通过对_2和Liq的分子空间结构与性能进行分析与讨论,发现_2是通过两个Na-O-Na键桥将两个Liq和两个Naq连接构成的,其分子平面结构的刚性程度强于Liq,空间位阻大于Liq,分子之间的距离大于Liq,分子极性远远小于Liq;_2的荧光寿命长于Liq,荧光量子效率高于Liq,成膜性优于Liq;_2的禁带宽度比Liq大,光致发光光谱中_2的最大发射峰较Liq发生蓝移;当_2在OLED中作为发光层时,激发二聚体与激基复合物的生成几率远远小于Liq,发的光比Liq更蓝,电流效率大于Liq;_2超薄膜中有Na离子的存在,与Liq超薄膜相比,当其在OLED中作为电子注入层时,具有更大的电流密度,更高的发光强度,更低的阈值电压和更高的电流效率 5、对上述Alq_3、Znq_2和Liq的分子空间结构与材料性能之间的关系进行了归纳总结,认为Mq_n的分子空间结构主要在分子平面结构的刚性程度,相邻分子之间的相互作用,分子堆叠的方式和分子之间的距离这四个方面影响其性能。

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