SYNTHESIS OF DIAZA CROWN ETHER CHIRAL LIQUID CRYSTAL

A chiral liquid crystal crown ether containing diaza-18-crown-6 was synthesized with the help of CPK atomic model and in the meantime a nonchiral liquid crystal crown ether of alike structure was also synthesized for comparison, indicating that only the former was asymmetric. The present work represents the first attempt of the investigation in chiral liquid crystal crown ether, thus providing basis for further research into problems as such.

Synthesis and Phase Behavior Studies of Two New Chiral Liquid Crystals of Schiff Base——The Influence of Intramolecular Hydrogen Bond on the Phase Behavior

Two new chiral liquid crystals of schiff-base type have been synthesized.This series of compounds contain α-chloro acidic ester chain prepared from commercially available L-valine.Both of the compounds exhibit tilted smectic phases;their phase transitions were studied using DSC and polarized optical microscopy;the influence of intramolecular hydrogen bonds on the phase behavior was studied as well.

Chiral liquid crystals based on pillararene and supramolecular self-assembly-induced chirality amplification

Macrocyclic liquid crystals combine the unique property of liquid crystals and excellent supramolecular assembly ability of macrocyclic compounds.It is a significant challenge to make rational use of the advantages of macrocyclic compounds to prepare new macrocyclic mesogens.Pillararenes,a type of macrocycles with rigid pillar-shaped frameworks and easy-tofunctionalize property,are excellent building blocks to fabricate liquid crystal materials.However,the site-selective modification property of pillararene has been rarely exploited to tailor liquid crystal behaviors.Previously reported pillararene-based liquid crystal systems are almost prepared by per-functionalized pillararenes.Herein,we report the regulation of chiral liquid crystal behaviors by different derivatization of pillararene.Lyotropic and thermotropic liquid crystals with different chirality were obtained by self-assembly of pillararene with different numbers of cholesterol groups.The bridge between thermotropic liquid crystal and lyotropic liquid crystal based on pillararene is built.In addition,the chirality of the mesogens can be amplified through supramolecular self-assembly driven by noncovalent interactions.Based on the different liquid crystal behaviors,the optical signal of the pillararene-based chiral liquid crystals was used to fabricate an information encryption system.This work provides a simple strategy to regulate liquid crystal behaviors via pillararene-based mesogens and realizes information encryption through the combination of different types of liquid crystals.

Field-induced phase transitions in chiral smectic liquid crystals studied by the constant current method

In ferroelectric liquid crystals, phase transitions can be induced by an electric field. The current constant method allows these transition to be quickly localized and thus the（E, T） phase diagram of the studied product can be obtained.In this work, we make a slight modification to the measurement principles based on this method. This modification allows the characteristic parameters of ferroelectric liquid crystal to be quantitatively measured. The use of a current square signal highlights a phenomenon of ferroelectric hysteresis with remnant polarization at null field, which points out an effect of memory in this compound.

STUDY ON MAGNETIC FIELD-INDUCED 0RIENTATI0N OF A CHIRAL SIDE-CHAIN LIQUID CRYSTAL POLYACRYLATE USING INFRARED DICHROISM

Magnetic field-induced orientation of a chiral side chain liquid crystalline polyacrylate(P-11) was studied by using IR dichroism. For the investigated P-11, it has been shown thatthe magnetic alignment takes place over the entire temperature range between its meltingpoint and clearing point and the orientation level is strongly temperature-dependent, thedevelopment with time of the magnetic orieatation follows an exponeotial-type relation,and the smectic phase state influences the thermal relaxation process in the absence of themagnetic field.

Synthesis and helical twisting property of polymerizable chiral dopant with temperature-dependent solubility in liquid crystal

In this study, right-handed dicinnamate isosorbide was synthesized via the esterification reaction betweefi optically active isosorbide and cinnamate. The chiral dopant was characterized by FT-IR, ^1H NMR, elemental analysis, SEM, UV absorption spectrum. After dissolving in a nematic liquid crystal mixture, the chiral dopant exhibited a temperature-dependent solubility in the chiral nematic liquid crystal mixture. Meanwhile, a relatively high value of helical twisting power of the polymerizable chiral dopant was determined. The results show that the chiral dopant has great potential in achieving a polymer stabilized chiral nematic liquid crystal film with a broad-band selective reflection. C 2009 Huai Yang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

SYNTHESIS AND CHARACTERIZATION OF NOVEL CHIRAL SMECTIC C(Sc~*) PHASE SHISH-KEBAB TYPE LIQUID CRYSTALLINE BLOCK COPOLYMERS

A new series of chiral shish-kebab type liquid crystal block copolymers that form the smectic C(Sc*) phase was synthesized by solution polycondensation. The copolymers were characterized by GPC, DSC, TG, POM, X-ray diffraction and polarimeter. The copolymers 7 entered into liquid crystal phase whin they were heated to their melting temperatures (T-m) and the copolymers 8 were in liquid crystal phase at room temperature with low viscosities. The smectic sanded texture or focal-conic texture were observed on POM. All the chiral block copolymers showed high optical activity. No racemization has happened. Temperature-variable X-ray diffraction study together with POM and polarimetric analysis realized that they are chiral smectic C(Sc*) phase. Thus we offer in this report the first example of shish-kebab type liquid crystal block copolymers that form a chiral smectic C(Sc*) phase. The variation of melting and isotropization temperatures with molecular structure was also discussed.

Synthesis and characterization of non-symmetrical liquid crystals containing a cholesteryl ester moiety

In this paper, a series of chiral non-symmetrical liquid crystals （nBA-chol） consisting of a cholesteryl ester moiety as chiral entity and a biphenyl aromatic core with different terminal alkyl chain has been synthesized and investigated for their liquid crystalline properties. Effects of numbers of methylene units in the terminal alkyl chain on the phase transition temperatures and on the temperature-dependent pitch lengths of the chiral liquid crystals have been studied. The long terminal alkyl chain tends to exhibit smectic A mesophases. The pitch lengths of the cholesteric mesophases of the chiral liquid crystals decrease with increasing temperature and with increasing numbers of methylene units in the terminal alkyl chain, respectively.

Influence of terminal alkyl chain length on helical twisting property of chiral 1,2-propanediol derivatives

In this study, a novel series of chiral 1,2-propanediol derivatives with different terminal alkyl chain length were synthesized and characterized by FT-IR, ^1H NMR and DSC. After doped into a nematic liquid crystal host, all the chiral dopants induced chiral nematic liquid crystals exhibiting a helix inversion with temperature variation. The results indicate that terminal alkyl chain length has a prominent influence on helical twisting property of the chiral dopants. With increasing the terminal alkyl chain length, the molecular twisting power increases, the helix inversion temperatures varies slightly while the phase transition temperature decreases. An odd-even effect may exist in the molecular twisting power of the chirai dopants.

UNUSUAL CRYSTALLIZATION AND MELTING PROCESSES OF AN OPTICALLY ACTIVE POLYOLEFIN:ISOTACTIC POLY((S)-4-METHYL-HEXENE-1)

Polyolefins that bear a chiral side chain(typically an isobutyl group)experience a so-called macromolecularamplification of chirality:the chiral side-chain induces a slight preference for either tg or tg(?) main chain conformation.Thisslight conformational bias is amplified cooperatively along the chain,and results in preferred chirality of the main chainhelical conformations.As a result,these polymers display a liquid-crystal(LC)phase both in solution and,in the melt as atransient phase on the way to crystallization.The existence of two processes(melt-LC and LC-crystal transitions)results inunconventional behaviors that were first analyzed by Pino and collaborators back in 1975.These polymers also offer a meansto test the structural consequences of recently introduced crystallization schemes.These schemes postulate the formation of atransient liquid-crystal phase as a general scheme for polymer crystallization.

胆甾相液晶色彩调制的研究性实验设计

胆甾相液晶的螺距能随材料配比、温度、外加电场等发生改变,进而对外界光进行调制。针对胆甾相液晶温致变色等现象,设计了研究性实验“胆甾相液晶色彩调制的研究性实验设计”,探究了胆甾相液晶材料的清亮点、织构、螺距和选择性反射随手性剂浓度和温度的变化规律。该实验流程完整,涉及材料配制、光学测量和性能检测,并将理论与实际应用相结合,有助于激发学生对温致变色材料的研究兴趣,培养学生创新性实验方案设计能力。

Synthesis and Properties of Some Novel Liquid Crystals: Chiral 4′-(4-alkoxy-2,3-difluorobenzoyloxy)-4-biphenyl Carboxylates

A series of laterally o difluoro substituted chiral liquid crystals, S(+) 2 methyl 1 butyl 4′ [(4 alkoxyl 2, 3 difluoro)benzoyloxy] 4 biphenyl carboxylates, have been synthesized using a simple process. Their molecular structures were determined using IR, NMR, MS, and EA. Their transition temperatures were measured using DSC(Differential Scanning Calorimeter). All of the compounds exhibit the N * phase and their clearing points vary regularly with the increase in the number of terminal group carbons. The influence of lateral fluoro substituents on the properties was also investigated.

近晶相液晶超结构的多元外场调控

利用液晶的自组装和刺激响应特性,实现近晶相液晶多层级超结构的灵活构筑、动态操控和多功能应用对于激发更多前沿的创新性功能器件并推动液晶超结构的实用化进程具有重要意义。本文从近晶相液晶超结构的生长制备、多元外界刺激对缺陷结构的调制方法和动态调控规律等方面进行系统研究。首先,探究了图案化取向场和旋涂条件对近晶相液晶拓扑超结构的形态与大小的操控;然后,验证了焦锥畴超结构的微透镜成像功能,并通过材料复合优化和引入聚合物稳定策略,实现了正方焦锥畴阵列在35℃下(向列相)的电刺激动态调控性能;最后,研究了手性、光场和热场对双相态液晶超结构带来的多维度调控。本研究充分利用光取向场、聚合物网络、电场、手性、光场等多元外场刺激,实现了对近晶相液晶多层级超结构的多维度调控。

基于双手性液晶超结构的自旋解耦彩色全息

随着人们对信息容量和色彩的要求日益提高,彩色光学全息术备受关注,目前已广泛应用于彩色显示、AR/VR、信息加密等领域。然而,目前的彩色全息术大多基于超表面等体系,在以液晶为代表的软物质中,实现彩色全息仍具有挑战性。本文提出一种上下分层的双手性胆甾相液晶超结构,结合液晶光取向和布拉格反射带调控技术,实现圆偏振复用的彩色全息。其中,利用表面诱导聚合的洗去-重填工艺和液晶光控图案化技术,实现了自旋解耦的几何相位,可对左右旋圆偏振光进行独立的相位调制。入射光只有在偏振、波长均与胆甾相液晶匹配时才能获得几何相位并产生全息图像,通过独立调控左右旋胆甾相液晶的布拉格反射带,在同一衍射面上成功产生了多种全息图像,可调的彩色复用全息得以呈现。本研究提出的基于双手性液晶超结构的自旋解耦彩色全息术有望助力先进显示、光学加密和多通道通信等领域。

聚乙二醇/纤维素纳米晶体复合液晶薄膜微观结构及湿度响应行为

【目的】探索聚乙二醇(PEG)对纤维素纳米晶体(CNC)液晶薄膜湿度响应的影响,阐明其响应机制,旨在为开发低成本、可重复使用和高灵敏度的PEG/CNC复合薄膜湿度传感器提供理论基础。【方法】将CNC与PEG共组装,制备了一种具有湿度响应性能的虹彩色手性向列相光子液晶薄膜,系统考察了PEG质量分数对液晶薄膜的微观结构、显色、力学性能及湿度响应的影响,在此基础上,研究了PEG/CNC复合液晶薄膜在不同湿度条件下的响应循环性能。【结果】对于纯CNC体系,CNC质量分数由3%增加到7%,CNC液晶薄膜的螺距减小,最大反射光波长由596.5 nm蓝移至511.0 nm;对于添加PEG的CNC体系,随着PEG质量分数的增加,PEG/CNC复合液晶薄膜的螺距由394.0 nm减小到244.0 nm,最大反射光波长由613.5 nm蓝移至350.5 nm,韧性先提升后下降,PEG质量分数为5%时为最佳,断裂能为31.9 J·m^(-2),较纯CNC薄膜提升了138%;液晶薄膜经过5次吸湿-解湿,表现出良好的湿度响应重复性,平衡波长的变化率小于0.6%。【结论】制备了一种对湿度具有敏感响应的虹彩色光子PEG/CNC复合液晶薄膜,PEG可以调控复合薄膜螺距,起到调节结构色的作用。

Entropy-driven self-assembly of chiral nematic liquid crystalline phases of AgNR@Cu20 hyper branched coaxial nanorods and thickness-dependent handedness transition

The chiral nematic liquid crystalline phase （CNLCP） of noble metal nanorods induces a strong chiroptical response due to their intrinsic physical and chemical properties. Here, we demonstrate that the formation of CNLCP of Ag nanorods （AgNRs） originates from their bent-shape and is the result of purely entropic effects. The chirality of the liquid crystalline phase of AgNR@Cu20 hyper branched coaxial nanorods （HBCNRs） can be switched from left-handed to right-handed by increasing Cu20 thickness. It is proposed that the increase of coating thickness decreases the curvature of nanorods, which induces variation of the twist constant （/〈2） and bend elastic constant （K3）. The increased thickness also changes the direction of director with respect to the helical axis. In addition, hydrogen bonds can break the CNLCP, which can be attributed to their stronger effection compared to van der Waals forces and electrostatic interactions. In contrast to the variation of coating thickness, the surface morpholog~ constituents of the hybrid building blocks and polarity of the solvents do not play important roles in the handedness transition of the liquid crystalline phase. Furthermore, the results presented here give insight into the structure-property relationship and our strategy provides guidance for the synthesis of other inorganic chiral suDrastructures driven bv entroDic effects.

Stereoselective Photochemical Reaction of Cyclohexyl Phenyl Ketone within Lytropic Liquid Crystals Formed by Chiral Ionic Liquids

Irradiation of cyclohexyl phenyl ketone （1） results in either intra- or intermolecular hydrogen abstraction to af- ford compounds 1-phenylhept-6-en-l-one （2） and a-cyclohexyl benzyl alcohol （3） as photoproducts, in which 3 has a pair of enantiomers. Herein, two types of chiral hexagonal liquid crystals were prepared to direct the enantioselec- tive photochemical reaction of 1. One of the hexagonal liquid crystals is composed of 1-tetradecyl-3-methyl- imidazolium bromide/p-xylene/H2O with the modification by a chiral inductor. The other one is formed by chiral （S）-3-hexadecyl-1-（1-hydroxy-propan-2-yl）-imidazolium bromide/p-xylene/H2O. The product analysis shows that the latter one can be used as a microreactor to achieve stereoselective photochemical reaction, while the former one produced compound 3 with no enantioselectivity at all.

两个新的氢键诱导液晶化合物的合成

通过４－丁氧基苯甲酸（４ＢＡ）与两个手性取代的苯乙烯基吡啶（ＶＳＺ及ＬＳＺ）间的氢键作用合成了２个新的液晶化合物，用ＤＳＣ、偏光显微镜研究了其液晶行为，并由红外光谱证实了分子间氢键的存在。形成的复合物４ＢＡ－ＶＳＺ具有手性近晶Ｃ相。

纳米粒网络对于手性液晶反射光谱的展宽效应

依据分子呈螺旋型排列的介质的电磁场解计算了给定厚度的手性液晶的光谱反射率与其双折射的关系,依据布拉格反射的干涉条件计算了斜入射光的布拉格反射光谱的蓝移。从中发现:(1)若液晶的双折射大于0.2,液晶层的厚度达到3μm就可使反射率高于90%;(2)若要以液晶的平面态实现整个光谱范围的布拉格反射,液晶的双折射应当达到0.6以上;(3)入射角达到60°时手性液晶的反射光谱蓝移可达到100nm。然而,商品手性液晶的双折射只有0.2左右,为了将这样的手性液晶用于在整个可见光谱反射的显示器件,就需要在液晶中引入聚合物网络,并在玻璃基片表面实现聚合物的凹凸结构。网络的作用是要在液晶层中建立随机分布的分子锚定机制,使手性液晶的螺距随位置而变化,从而展宽其布拉格反射谱。基片表面的凹凸结构用于诱导液晶螺旋轴的斜向随机分布,以利用倾斜螺旋结构布拉格反射的蓝移现象,进一步展宽布拉格反射谱。实验证明,在液晶中引入聚合物网络和表面的凹凸结构以后,手性液晶的布拉格反射区间由原来的80nm增加到120nm以上,对比度达到4∶1左右。

芳环上氟原子对手性液晶分子扭曲力的影响

通过Mitsunobu反应合成了一系列手性液晶,收率63%～71%,并通过1 H NMR、MS、IR对其结构进行了表征。结合DSC和POM研究了目标化合物的介晶性。利用Cano's wedge法研究了目标化合物的扭曲力,发现随着手性中心邻近芳环上氟原子数的增多,手性液晶分子的扭曲力显著增大。实验结果表明,氟原子的引入影响了碳氧单键的自由旋转,导致手性液晶分子具有较少构象异构体,从而表现出大的扭曲力。