丙烯酸酯封端的取代氢键液晶的制备及性能研究

合成了3种丙烯酸酯封端的取代苯甲酸以及其分别与4, 4′-联吡啶和反式吡啶基乙烯自组装形成的双氢键液晶,采用傅立叶红外光谱(FTIR)和核磁共振法(~1H-NMR)表征化合物的结构,使用偏光显微镜(POM)以及差示扫描量热仪(DSC)研究氢键液晶复合体的相转变行为.结果表明,在刚性液晶基元中引入氟原子会增加氢键液晶分子的宽度和降低分子的长径比对液晶材料的性能有很大影响,如降低氢键液晶的熔点以及清亮点等.另外,在柔性链末端引入丙烯酰氧基以及增加液晶基元的长度则会增加液晶分子的长度和规整性,提高氢键液晶复合体的相转变温度.     

分子间氢键自组装手性液晶的变温红外研究(英文)

通过存在于吡啶环和羧基间的分子间氢键自组装合成液晶已逐渐引起科学工作者的重视,决定这种方法是否适用的关键是分子间氢键的稳定性。由于变温红外光谱能很好地反映出液晶分子环境的变化,尤其是分子中羰基基团对分子环境变化,对分子内和分子间的相互作用更为敏感,并且又能反映出这种分子间氢键的稳定性。因此本文研究了通过存在于4—[(2S)—2—氯—3—甲基—丁酰氧基]—4′—苯乙烯基吡啶(MBSB)和4—烷氧基苯甲酸(nBA,n=5,6)问的分子间氢键自组装的两个手性液晶(nBA:MBSB)的变温红外光谱。研究结果表明nBA:MBSB中的酯羰基基团对于K—Sc*转变极为敏感,对Sc*—S_A和S_A—N转变不敏感,同时结果表明分子间氢键在晶体和液晶态是稳定的,并且这种分子间氢键强于存在于羧基和羧基间的氢键,因此这种存在于羧基和吡啶环间的氢键为液晶分子设计提供了又一条有效的途径。     

胆甾液晶应用于P3HT∶PCBM聚合物光伏器件研究

本研究利用液晶材料的自组装特性,将胆甾醇油酸酯3β-Hydroxy-5-cholestene 3-oleate掺杂有机聚合物太阳能电池活性层P3HT:PC61BM内,制备出不同掺杂比例的光伏器件。实验结果表明,液晶掺杂质量比为0.3%时,器件的光电转换效率最高。说明液晶分子可诱导活性层材料分子在结晶过程中有序排列,减少层内分子团簇,减少活性层薄膜缺陷,形成有效的载流子传输通道。适当的掺杂比例,增大了器件并联电阻和填充因子,器件性能得到改善。     

氢键组装的超分子液晶的研究进展

介绍了近十几年来典型的氢键组装的超分子液晶材料的组装方法和分子结构,对比其光电性能和自组装特点,并对其在光电器件方面的应用进行展望。这类材料依据氢键组装的方式和分子结构主要分为两大类:结构封闭型和结构开放型。与后者相比,前者具有易于结构修饰和易于精确调控性能的特点。但两者内部的分子结构变化时,组装的超分子液晶材料的性能均受到显著影响。分子间氢键作用组装的超分子液晶材料具有高度有序性和可精确调控性,因此作为新型材料在有机光电器件和纳米器件等领域具有广阔的应用前景。     

西佛碱和偶氮液晶冠醚的合成(英文)

由中间体顺(反)—4,4′一二氨基二苯—18冠—6和4′氨基苯—15冠—5首次合成了六种西碱和偶液晶冠醚,通过元素分析,IR,~1HNMR和MS确证了它们的结构,并通过DSC和织构图测定了它们的液晶性质。探讨了双臂冠醚和单臂冠醚与液晶性质的关系,认为当双臂冠醚的分子L/D在4—8,单臂冠醚的L/D大于3时它们才具有液晶性质。此结论与作者过去的研究结果一致。     

氢键诱导胆甾相液晶化合物的合成(英文)

本文通过存在于胆甾醇丁二酸单酯(MCB)和4—(4—烷氧基苯甲酰氧基)—4′—苯乙烯基吡啶(nSZ)间的氢键作用合成了一系列新的胆甾型液晶,其液晶行为通过DSC、偏光显徽镜及变温广角X光衍射等手段进行研究。对于nSZ:当n≤3时,仅呈现向列相;当n=4,5时,呈现近品A相和向列相;当n＝6,7时,还出现一种单变的近晶相(S相);当n≥8时,向列相不存在,只呈现近晶A相和单变的S_1相。MCB不是液晶,而两者的1:1复合物均呈现互变的近晶C相和胆甾相,并且当n≤3时,nSZ:MCB的相变区间比nSZ的相变区间宽。X光衍射结果表明,7SZ扣8SZ的层厚度(d值)比基分子全伸展理论长度要长,这意味着这种不含强极性基团(如硝基、氰基)的液晶分子呈双层排列。     

利用香蕉形液晶自组装技术研制有机无刻痕光栅

通过有机合成,获得了香蕉形分子液晶材料1,3-phenylenebis(4-butyloxy-benzylideneamine)。用核磁共振谱仪、紫外光谱仪、元素分析仪、偏光显微镜、差热扫描量热分析仪、激光衍射实验等分析技术,对所合成的香蕉形液晶材料进行了细致的表征。结果表明:这些香蕉形分子能够通过分子自组装技术而形成各种各样的、双折射率周期性变化的规整结构。尽管无刻痕,氦氖激光衍射实验表明,由香蕉形液晶分子自组装而成的光栅能够像有刻痕光栅那样对红光进行有效衍射。     

氢键复合物中间相行为的变温红外光谱研究

在差示扫描量热仪(DSC)和偏光显微镜(POM)的辅助下,采用变温红外光谱对所制备的基于4,4′-联吡啶(BPy)和4-丙基苯甲酸(PBA)、4-丙基反式环己基甲酸(PCA)的氢键超分子复合物PBA-BPy和PCA-BPy中的氢键的热稳定性进行了研究.结果表明,超分子PBA-BPy中的氢键非常稳定,甚至在温度高于它的清亮点时氢键也不分解;而对于PCA-BPy,情况则完全不同,当温度稍高于它的熔点时,其分子中的氢键就被破坏.这一结果解释了为什么在结构类似的情况下PBA-BPy具有近晶相和向列相行为而PCA-BPy不具有任何中间相特征.     

聚合工艺对联苯侧链型聚酰亚胺薄膜取向性能的影响

以4,4′二氨基二苯醚(ODA)、 3,5-二氨基苯甲酸{6-[4′-(苯基)苯氧基]}己基)酯(C6-DABBE)、4,4′-二苯醚四羧酸二酐(ODPA) 为单体,分别采用一步法和两步法共聚合成一系列含有联苯侧链的聚酰亚胺.采用衰减全反射红外光谱(ATR-FTIR)、表面能、原子力显微镜(AFM)、光电子能谱(XPS)等测试手段对薄膜的基本性能进行了研究.通过对预倾角的测量考察了液晶分子在联苯侧链聚酰亚胺薄膜上的取向性能.结果表明,一步法和两步法合成的聚酰亚胺表面分子结构基本一致,都能使液晶分子表现出良好的取向性能;液晶分子的预倾角随着聚酰亚胺侧链含量的增加而增加;由于两步法更有利于侧链在表面富集,所以采用两步法可获得更大的预倾角.     

极性自组装单层膜取向铁电液晶器件

采用极性自组装单层膜和摩擦的方法制备了非对称的液晶盒.在铁电液晶相变的过程中不施加电场,得到了排列均一的铁电液晶器件.实验表明:极性自组装单层膜极性越大器件的对比度越高.经过分析得出该器件液晶分子取向机理为:基板附近的铁电液晶通过偶极和极性自组装膜的作用,使得靠近自组装膜表面处的偶极和靠近摩擦表面的偶极的指向相同,通过分子的相互作用使得体内分子排列方向一致.     

含氟二苯乙炔类蓝相液晶的研究进展

蓝相液晶具有高度流动的自聚集的三维立方缺陷结构,在高度手性的液晶中,它们存在于狭窄的温度区间。分子中引入适当的手性中心可以制得蓝相液晶。由于氟原子的特殊性,在液晶核分子中引入含氟二苯乙炔,可以得到黏度低、双折射率及清亮点高的液晶材料。文中介绍了6类含手性端基的含氟液晶化合物(其中有一个化合物不含氟原子)。通过偏光显微镜和DSC对其相变行为进行了研究。结果表明:共有13个化合物显示蓝相;化合物结构中手性中心的细微差别都会导致蓝相的出现或消失。     

基于分子间氢键的棒状手性液晶的研究进展

分子间氢键棒状手性液晶因其兼具手性液晶奇特的光电性能和氢键液晶的便捷制备以及独特的外界刺激响应性,在功能材料、非线性光学、生物医学等领域具有潜在的应用价值,一直是超分子液晶领域的研究热点。文章按照形成氢键互补基团的不同,将其划分为3种类型,即羧酸-羧酸类、羧酸-吡啶类和其他类型氢键,介绍了此三类氢键棒状手性液晶近年来的研究进展。详细归纳了氢键质子给受体的分子结构、氢键稳定性、手性中心位置、取代基、柔性链长度等对液晶性能的影响,并在此基础上,对其未来发展做了展望。     

Mechanomorphogenic Films Formed via Interfacial Assembly of Fluorinated Amino Acids

Nature has evolved several elegant strategies to organize inert building blocks into adaptive supramolecular structures. Favored among these is interfacial self-assembly, where the unique environment of liquid–liquid junctions provides structural, kinetic, thermodynamic, and chemical properties that are distinct from the bulk solution. Here, antithetical fluorous–water interfaces are exploited to guide the assembly of non-canonical fluorinated amino acids into crystalline mechanomorphogenic films. That is, the nanoscale order imparted by this strategy yields self-healing materials that can alter their macro-morphology depending on exogenous mechanical stimuli. Additionally, like natural biomolecules, organofluorine amino acid films respond to changes in environmental ionic strength, pH, and temperature to adopt varied secondary and tertiary states. Complementary biophysical and biochemical studies are used to develop a model of amino acid packing to rationalize this bioresponsive behavior. Finally, these films show selective permeability, capturing fluorous compounds while allowing the free diffusion of water. These unique capabilities are leveraged in an exemplary application of the technology to extract perfluoroalkyl substances from contaminated water samples rapidly. Continued exploration of these materials will advance the understanding of how interface-templated and fluorine-driven assembly phenomenon a can be co-utilized to design adaptive molecular networks and living matter.     

Parallel Polar Dimers in the Columnar Self-Assembly of Umbrella-Shaped Subphthalocyanine Mesogens

The self-assembly of umbrella-shaped mesogens is explored with subphthalocyanine cores and oligo(thienyl) arms with different lengths in the light of their application as light-harvesting and photoconducting materials. While the shortest arm derivatives self-assemble in a conventional columnar phase with a single mesogen as a repeating unit, the more extended derivatives generate dimers that pile up into liquid crystalline columns. In contrast to the antiparallel arrangement known from single crystals, the present mesogens align as parallel dimers in polar columnar phases as confirmed by X-ray scattering, experimental densities, dielectric spectroscopy, second harmonic generation, alignment, and conductivity studies. UV–vis and fluorescence spectroscopies reveal a broad absorption in the visible range and only weak emission of the Q-band. Thus, these light-collecting molecules forming strongly polar columnar mesophases are attractive for application in the area of photoconductive materials.     

Hydrogen‐Bonded Liquid Crystals in Confined Spaces—Toward Photonic Hybrid Materials

A series of hybrid materials based on chiral nematic mesoporous organosilica (CNMO) films infiltrated with liquid crystalline hydrogen‐bonded assemblies is prepared and characterized with respect to the mutual manipulation of the photonic properties of the host and the liquid‐crystalline behavior of the guest. Detailed differential scanning calorimetry studies reveal the impact of confinement on the mesomorphic behavior of the liquid crystalline assemblies in the pores of the CNMO films. The photonic properties of the chiral nematic mesoporous host can be controlled by changing the temperature or irradiating the films with UV light. These stimuli‐induced phase transitions are accompanied by changes in the orientational order of the mesogens as revealed by ¹⁹F NMR spectroscopy. The combination of confinement and changes in the molecular orientation in a unique hybrid material based on hydrogen‐bonded liquid crystals and a porous host with a chiral nematic mesostructure is an interesting concept for the design of optical sensors, reflectors, or filters.     

含希夫碱基团的不对称弯曲型液晶分子的合成和相变研究

以3-氨基-2-甲基苯甲酸为原料,合成了含希夫碱基团的5个不对称弯曲型液晶分子,通过1HNMR、HRMS测试手段对其结构进行了表征,采用示差扫描量热法(DSC)和偏光显微镜等方法研究了它们的液晶性和相变温度,发现不仅相变温度随着分子苯环数的下降而下降,其液晶相的稳定性也随着苯环数的下降而下降,含有5个苯环的化合物呈现多个近晶相和向列相,含4个苯环的化合物则只有一个近晶相和向列相,而3个环的化合物仅在降温的过程中呈现近晶相。     

含胆甾烯基结构的手性二介晶结构液晶化合物

二介晶结构液晶化合物是指分子中含有由柔性的间隔基连接2个同样的介晶结构单元（对称）或不同的介晶结构单元（不对称）的化合物。对称的二介晶结构化合物可作为高分子液晶研究的理想模型，而不对称的二介晶结构化合物，尤其是含胆甾烯基结构的二介晶结构液晶化合物由于胆甾烯基的手性呈现新型而独特的液晶相，并且其液晶行为随着连接2个介晶结构单元的间隔基的碳链长度和碳原子数的奇偶以及第二个液晶结构单元的种类有规律性的变化，引起了各国学者的关注。本文总结了含胆甾烯基结构的手性二介晶结构液晶化合物的液晶性质。     

Properties and applications of liquid crystals

This paper is a brief review of some of the properties and applications of liquid crystals. References will guide the reader to more extensive presentations. Molecular geometry is important in interpreting the properties of liquid crystals. Certain aspects of molecular geometry are discussed along with classification of the different types of liquid crystals. The molecular packings in some liquid crystalline structures are presented and correlated with some of the behaviors of the liquid crystalline state of matter. Optical properties which relate to applications of liquid crystals are described. Applications of liquid crystals are focused on three common areas. These include the use of cholesteric materials (spontaneously twisted nematic liquid crystals) in non-destructive testing in industrial laboratories and in medical clinics; the use of liquid crystals in displays; and the use of liquid crystals as solvents.     

高性能热致液晶聚合物LCP基板卷材开发与应用

文章采用4-乙酰氧基苯甲酸（ABA）6-乙酰氧基-2-萘甲酸（ANA）共缩聚合加入4,4、二氨基二苯醚（ODA）聚醚酰亚胺（PEI）,通过刚性棒状大分子链受热熔融形成一种兼有固体和液体的部分性质的液晶态聚合物通过涂布延伸,二阶段溶浸聚合溶融缩聚制备LCP基板卷材。     

Charge Transportation and Chirality in Liquid Crystalline Helical Network Phases of Achiral BTBT-Derived Polycatenar Molecules

First examples of multichain (polycatenar) compounds, based on the π-conjugated [1]benzothieno[3,2-b]benzothiophene unit are designed, synthesized, and their soft self-assembly and charge carrier mobility are investigated. These compounds, terminated by the new fan-shaped 2-brominated 3,4,5-trialkoxybenzoate moiety, form bicontinuous cubic liquid crystalline (LC) phases with helical network structure over extremely wide temperature ranges (>200 K), including ambient temperature. Compounds with short chains show an achiral cubic phase with the double network, which upon increasing the chain length, is at first replaced by a tetragonal 3D phase and then by a mirror symmetry is broken triple network cubic phase. In the networks, the capability of bypassing defects provides enhanced charge carrier mobility compared to imperfectly aligned columnar phases, and the charge transportation is non-dispersive, as only rarely observed for LC materials. At the transition to a semicrystalline helical network phase, the conductivity is further enhanced by almost one order of magnitude. In addition, a mirror symmetry broken isotropic liquid phase is formed beside the 3D phases, which upon chain elongation is removed and replaced by a hexagonal columnar LC phase.