CuW_(11)Cd/PANI掺杂材料的制备、表征及光催化性能

采用化学氧化法制得K_8[CuW_(11)CdO_(40)]/PANI掺杂材料,并用IR、UV、XRD、EDS、SEM对所合成的掺杂材料进行了表征。并利用所合成K_8[CuW_(11)CdO_(40)]/PANI掺杂材料为催化剂,研究了对亚甲基蓝溶液光降解催化活性。通过实验确定了光降解的最佳条件为:亚甲基蓝溶液初始pH为2,亚甲基蓝溶液初始浓度为10mg·L~(-1),催化剂用量为0.08 g,在光照100 min,亚甲基蓝溶液的脱色率为98.11%。因此,K_8[CuW_(11)CdO_(40)]/PANI掺杂材料是一种很好的光降解催化剂。     

亚酞菁的合成及其光谱性质

亚酞菁是由 3个异吲哚联接 (酞菁是由 4个异吲哚联接 ) ,整个分子呈现出锥形结构[1] .尽管亚酞菁不是平面型分子 ,但它表现出离域的 1 4π电子体系 ,有芳香性 [2 ]而且化学稳定性、热稳定性好 ,也具有非线性光学性质等与酞菁类似的性质 [3 ] .虽然亚酞菁很早就合成出来 ,但有关它的光学及其它性质的研究仍然较少 ,直到 90年代才开始报道 ,其主要原因是提纯非常困难 ,甚至现在许多已报道的合成路线都难以重现 ,因为许多亚酞菁溶解度较差 .人们主要利用亚酞菁来合成不对称酞菁 [4 ] .应用亚酞菁可作有机光导体 [5] ,有机电致发光材料 [6] ,光…     

富勒烯配合物η2-C60[Ru(NO)(PPh3)]2的合成与表征

从1985年Kroto等[1]发现富勒烯至今, 其在化学、材料和物理等领域已有较多的研究[2～8]. 目前有关C60取代的金属小分子配合物(如羰基、亚硝酰基等)的研究方兴未艾. 而以NO为配体的亚硝酰基金属富勒烯配合物仅有数例[2,3], Green等[3]在研究以CO和NO为配体的金属富勒烯系列化合物的合成中, 认为C60不能与Ru(NO)2(PPh3)2发生反应. 本文利用Ru(NO)2(PPh3)2与C60反应首次合成出η2-C60[Ru(NO)(PPh3)]2配合物, 并对其进行了表征.     

K_8[Cd(H_2O)NiW_(11)O_(39)]/PANI掺杂材料的制备、表征及光催化性能

采用化学氧化法将Keggin结构K8[CdNi(H2O)W11O39]掺杂到聚苯胺中制得K8[CdNi(H2O)W11O39]/PANI掺杂材料,并用UV,IR,XRD,SEM和EDM等测试方法对掺杂材料进行表征.并研究了所合成掺杂材料催化剂为对亚甲基蓝溶液光降解催化活性.通过控制不同的影响条件,寻找光降解的最适条件,实验结果表明:掺杂材料具有很高的催化活性,最适条件下,110min内对亚甲基蓝溶液的脱色率达到99%以上,因此,[CdNi(H2O)W11O39]/PANI掺杂材料是一种很好的光降解催化剂.     

含三嗪或查尔酮结构聚对亚苯基亚乙炔基的合成及其荧光特性

聚对亚苯基亚乙炔基(polyphenyleneethynylene,PPE)是主链由苯环与乙炔基交替相联的线型聚合物,其共轭主链的电子流动性好,在溶液中有较高的荧光量子效率,具有独特的光电性能,已在分子导线、分子传感器、液晶显示、发光二极管和能量传输材料等领域得到应用[1~4].在聚对亚苯基亚     

高度可溶聚苝酰亚胺材料的合成及性能研究

聚酰亚胺是一类具有优异综合性能的聚合物材料 [1,2 ] .近年来 ,合成含荧光染料的可溶性聚酰亚胺材料在聚合物化学领域引起了广泛兴趣 [3～ 11] ,人们期望这类聚合物材料会比其小分子材料具有更加优越的性能 .小分子酰亚胺荧光染料具有极高的荧光量子效率、光化学和热稳定性 ,可广泛应用于光学开关[12 ] 、电致发光器件 [13,14 ] 和太阳能转换器 [15] 等领域 ,但是由于的大π键平面共轭结构 ,使得材料的溶解性能极差 ,难以加工 .最近 ,本实验室通过合成含叔丁基的芳香二胺 [4,4′-亚甲基双 ( 2 -叔丁基苯胺 ) ]与各种芳香四酸二酐反应…     

三甲基镓与氨基亚甲基酚配合物的合成与表征

八十年代以来,由于发现铝、镓、铟的金属有机化合物在制备半导体材料、特种陶瓷和电致发光材料等方面具有重要的应用价值 [1],因此,对此类化合物的研究报道也逐渐增多。 IIIA族金属有机配合物由于成键结构复杂,可以调节的结构点多,具有丰富的化学内含,而又具有相对稳定的化学性质 [2],所以,通过对 IIIA族金属有机配合物的研究,可以寻找到更稳定的、性能更佳的 MO(Metal Organic)新源,对于 MOCVD(Metal Organic Compound Vapor Deposit)技术的发展有着重要的意义 [3]。氨基亚甲基酚或萘酚由于其作为染料 [4]、杀虫剂 [5]、…     

非两亲性四硫代富瓦烯导电LB膜的研究

近年来，利用LB技术制备电活性的有机超薄膜受到广泛的关注．导电LB膜的膜材料主要是含有受体化合物7，7’，8，8’-四氰基二亚甲基苯醌（TCNQ）的电荷转移复合物[1~3]以及给体分子[4，5]，特别是四硫代富瓦烯（TTF）衍生物[6~8]．尽管LB膜多由带长链的两亲性分子组装而成，但是对非两亲性TTF衍生物LB膜的研究[9~11]结果表明，引入长链烷基并非制备TTF类电荷转移复合物LB膜的先决条件．该结果极大地拓展了LB膜材料的研究范围．本文报道非两亲性TTF衍生物与花生酸混合导电LB膜的制备、结构表征与导电性能研究．1实验部分利用亚磷…     

铕基金属有机框架材料从混合染料中选择性分离亚甲基蓝

利用紫外-可见吸收光谱和粉末X射线衍射等技术, 通过染料吸附实验、 混合染料吸附实验、 吸附动力学实验和循环吸附实验, 研究了一种铕基金属有机框架材料从混合染料水溶液中选择性分离亚甲基蓝的性能与机理. 研究结果表明, 该材料对亚甲基蓝的最大吸附量为20 mg/g, 在12 h内可完成对亚甲基蓝的选择性吸附, 且可以循环使用3次以上. 混合染料吸附实验结果表明, 该材料的吸附选择性源于孔道的静电作用与尺寸排斥效应.     

亚酞菁的合成、性质与应用研究进展

亚酞菁是酞菁缩环衍生物的典型代表,表现出新颖的锥形结构、优异的发光性质和丰富的可调控性,是一类有研究前景的新型荧光染料.研究证明通过对亚酞菁轴向、外围或中心环结构的简单修饰,可以有效调控其物理化学性质,如溶解性、吸收/荧光发射、荧光量子产率、单线态氧产率等,近年来引起了化学工作者的广泛关注.介绍了亚酞菁的结构、性质和研究意义,重点综述了亚酞菁的合成、结构和性质的关系及其在生物化学、材料化学和环境化学等领域的应用进展.最后对亚酞菁的发展现状做了简要总结,并对亚酞菁的发展进行了展望.     

含芴共轭单元的超支化聚合物的合成及表征

以芴和季戊四醇为初始物,分别合成了具有芴共轭单元和季戊四醇多臂结构的两种聚合单体,进一步采用Suzuki反应合成出一种结构新颖的部分共轭结构的超支化聚合物.利用紫外吸收光谱和荧光发射光谱对聚合物予以表征,结果表明,超支化聚合物具有与模型化合物分子相似的发光行为,既可以发出纯正的蓝光,又表现出支化结构对荧光发射的影响.差...     

Triazatruxene-containing hyperbranched polymers: Microwave-assisted synthesis and optoelectronic properties

Hyperbranched polymer structures represent a class of high-functionality building blocks with excellent three-dimensional topology for the construction of highly substituted conjugated polymers. In this contribution, an efficient microwave synthesis protocol toward the synthesis of conjugated hyperbranched polymers is presented. A novel series of soluble hyperbranched polyfluorenes (PTF1-PTF3) incorporating triazatruxene moiety as the branch units with various branching degrees have thus been successfully constructed with good yields and high molecular weight via a facile “A2+B2+C3” approach. The structures of the hyperbranched polymers were confirmed by NMR and GPC. Their thermal, optical, and electrochemical properties of the hyperbranched polymers were also investigated. The results showed that introduction of triazatruxene units into the hyperbranched structure endowed the polymer with good thermal stability and highly amorphous properties. Photophysical investigation of PTFx revealed strong blue emission in both solution and solid states. Hyperbranched polymers with higher degree of branching and proper content of linear fluorene units exhibited better photophysical properties in terms of narrow emission spectra and relatively high quantum efficiency as well as improved thermal spectral stability. The triazatruxene branching unit also played a role in raising the HOMO energy levels relative to those of polyfluorenes that would help to improve the charge injection and transport properties. The incorporation of triazatruxene unit into hyperbranched polymers has thus explored an effective avenue for constructing optoelectronic polymers with improved functional characteristics.     

Convenient Synthesis and Enhanced Second-order Nonlinear Optical Property of a Novel Hyperbranched Polymer

A novel hyperbranched polymer （3） was prepared by copolymerization of tri-aldehyde moieties with azo chromophores having two active methelene groups, from ＂A2＋B3＂ approach based on simple Kneovenagel reaction. For comparison, its analogue linear polymer （5） was also synthesized. The two polymers are soluble in common organic solvents, and exhibit good thermal stability. Interestingly, the hyperbranched polymer demonstrates dramatically enhanced second-order nonlinear optical property with comparison to its linear analogue.     

基于超支化聚合物的单分子胶束的研究进展

近年来,单分子胶束/粒子(Unimolecular micelle:UIM)引起了人们的极大兴趣,这是由于通过对核和壳的化学设计,粒子的溶解性、生物相容性、刺激响应性、与基质的相互作用等都可得到改进,粒子还可以包裹多种客体。相对于自组装法而言,超支化聚合物法在合成UIM方面具有某些独有的特征,主要表现在:(1)UIM的尺寸主要由超支化聚合物决定,从而具有相当的可预见性;(2)可以大规模、高浓度合成UIM;(3)对聚合物的亲水性没有要求,可以利用的聚合物非常广泛,核-壳结构更为丰富;(4)产品可以以任何形式存在。本文在简要比较以自组装法和超支化聚合物法合成UIM的基础上,主要介绍了以超支化聚合物(特别是超支化聚甘油醚(PG))为支架合成各种核-壳聚合物及其应用。以长链小分子或聚合物改性的PG可以用作纳米胶囊,也可以作为纳米模板来合成各种无机粒子,而后者显示出量子限制效应和模板效应。特别地,一种全亲水壳交联的、刺激响应的粒子的合成显示了超支化聚合物法在合成复杂UIM方面的优势。总之,超支化聚合物法提供了巨大的核-壳结构分子设计空间,为合成功能集成粒子提供了更多机会。     

Dual‐emissive polydiphenylsilane nanocomposite: effect of N,N′‐bis(4‐hydroxysalicylidene)‐1,2‐phenylenediamine‐Zn complex

The fluorescence properties of polysilane can be strongly influenced by creating new excited states that involve electronic transitions and the relaxation to the ground state. This work presents the optical effects obtained by doping a specially designed polydiphenylsilane copolymer with Zn complex of N,N′‐bis(4‐hydroxysalicylidene)‐1,2‐phenylenediamine. The nanocomposites have been prepared in solution by mixing the polymer with low amounts of Zn–salophen and using tetrahydrofuran as solvent. The ultraviolet–visible spectrum has shown the occurrence of an intermolecular charge transfer between polysilane and the metal complex. Photoluminescence studies have revealed an interesting dual emission profile of nanocomposite. The origin of this phenomenon has been evidenced by molecular modeling and simulation of the electronic transitions. The modeling results have unveiled a new low‐lying excited state due to intermolecular interactions. The thin films of nanocomposites have been drop‐casted from solutions. The obtained films have been studied by Transmission Electron Microscopy (TEM)‐Scanning Transmission Electron Microscopy (STEM)‐Energy Dispersive X‐ray analysis (EDX) to gain information on the film‐forming capacity and surface morphology. The results have revealed a high potential of such materials for fluorescence sensing applications. Copyright © 2015 John Wiley & Sons, Ltd.     

Tuning the optical properties of hyperbranched polymers through the modification of the end groups

Dye‐capped, hyperbranched, conjugated polymers were prepared by the modification of the peripheral bromo end groups of the hyperbranched polymer core with a palladium‐catalyzed Suzuki–Miyaura cross‐coupling reaction. The dye‐modified, hyperbranched polymers had high molecular weights and displayed good solubility in common organic solvents such as tetrahydrofuran, toluene, and chloroform. The structure of the dye‐modified, hyperbranched polymers was characterized by ¹H and ¹³C NMR and elemental analysis. The thermal properties of five kinds of hyperbranched polymers were investigated with thermogravimetric analysis and differential scanning calorimetry. The optical properties of the dye‐capped, hyperbranched polymers were investigated with ultraviolet‐absorption and fluorescence spectroscopy. The hyperbranched structure could effectively reduce the aggregation of the peripheral dyes. The emission colors of the hyperbranched polymers could be easily tuned by end‐group modification. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 111–124, 2007     

由4',4''-二羟基-2-甲酸－三苯基甲烷及其衍生物制备高碳超支化芳香聚酯

合成了一系列含羟基和乙酰氧基的超支化聚酯,将4',4'二羟基-2-甲酸－三 苯基甲烷（酚酞啉）直接缩聚和将4~＇,4~＂-二羟基-2-甲酸－三苯基甲烷进行酯 交换反应都成功得到了超支化聚酯,以PS作标准物,由GPC测得的重均分子量为 2000到8000,~13C NMR测试表明聚合物支化度略高于50%,聚酯的玻璃化转变温度 依赖于末端和侧基官能团类型,该超支化聚酯末端含有反应性官能团,具有类似线 性高分子的高的热稳定性,相比之下,由于其大分子的形状和官能团的影响,末端 为乙酰氧基的超支化聚枉费显示了优良的溶解性能,这与一般线性高分子大不相同 ,由于氢键的存在,末端为羟基的超支化聚酯的溶解性能不佳,但是酸酯显示了 优良的溶解性能,这与一般线性高分子大不相同,由于氢键的存在,末端为羟基的 超支化聚枉费的溶解性能不佳,但是酸化可破坏氢键网络,得到的超支化聚酯可深 于一般有机溶剂。     

Cinnamate-functionalized hyperbranched polymer as liquid crystal photo-alignment layer

In this work, 4-methoxylcinnamoyl chloride was reacted with a commercial hyperbranched polymer （Boltom-TM H30） to prepare a hyperbranched photosensitive polymer （H30-Ci）. The polymer was characterized by UV absorption spectrum and 1H- NMR spectrum. After processed by Linearly Polarized Polymerization （LPP） method, the spin-coated films of H30-Ci were used as photo-alignment layers to assemble liquid crystal （LC） cells containing nematic liquid crystal （5CB）. The observation by polarized microscope showed that the H30-Ci blended with a linear polymer （BP-AN-Ci） photo-alignment layers could align LC molecules in a very uniform way.     

聚硅烷高分子化学的发展及应用

本文介绍了聚硅高分子的合成方法、紫外吸收、光敏性、导电性等一系列特殊性质,聚硅烷高分子的化学反应以及聚硅烷材料的应用.     

Investigation of the conformation of hyperbranched poly(arylene oxindole)s using hyper‐Rayleigh scattering

A hyperbranched poly(arylene oxindole), a poly(methacrylate), and a dendrimer, to which the same nonlinear optical chromophore was attached via a small, rigid spacer, were prepared. The difference in hyper‐Rayleigh scattering intensities was measured and compared. From this study, it was concluded that the chromophores, and hence the functional groups in the macromolecule before functionalization, are orientationally correlated in the dendrimer, whereas they are not in the linear and hyperbranched polymer. More in particular, the chromophores in the dendrimer are fixed in a centrosymmetric way because of the globular structure, whereas there is no orientational correlation between the chromophores in linear and hyperbranched polymer. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3740–3747, 2009