Dimeric liquid crystalline compounds having a central malonic acid moiety: effect of the length of the spacers and terminal chains

We have studied the liquid crystalline properties of two new series of dimeric compounds consisting of a central malonic acid moiety, polymethylene spacers, and Schiff's base mesogens. In the first series we changed the length of the spacers with the terminal chain fixed as the butoxy group; in the second series we changed the length of the terminal alkyl or alkoxy groups while keeping the spacers fixed as decamethylene groups. In the first series, as the length of the spacer increased, the tendency to form smectic phases grew. In the second series, changing the alkyl terminal chain to the alkoxy terminal group raised the melting and isotropization temperatures. Increasing the length of the terminal group diminished the temperature range for the higher temperature smectic phase. The smectic phases are assigned to be smectic A and crystal smectic E phases.     

New possibility for an organic semiconductor: a smectic liquid crystalline semiconductor having a long conjugated core and two long alkyl chains

We report a new possibility for liquid crystalline organic semiconductors. These materials exhibit smectic liquid crystalline phases, in which the molecules assume a smectic molecular order by self-assembly. Because of the strong dispersion force among long alkyl chains, on cooling, smectic molecular order was retained at room temperature. A charge transport ability was also retained. The conductivity of a device having smectic liquid crystalline order is about 5×10⁷ that of a device with no smectic order. The current - voltage characteristic of the device has a very sharp increase at low threshold voltage (5 V). A high carrier mobility of 1.8×10^-2 was observed in the smectic phase of one of the compounds studied (e).     

New possibility for an organic semiconductor: a smectic liquid crystalline semiconductor having a long conjugated core and two long alkyl chains

We report a new possibility for liquid crystalline organic semiconductors. These materials exhibit smectic liquid crystalline phases, in which the molecules assume a smectic molecular order by self‐assembly. Because of the strong dispersion force among long alkyl chains, on cooling, smectic molecular order was retained at room temperature. A charge transport ability was also retained. The conductivity of a device having smectic liquid crystalline order is about 5×10⁷ that of a device with no smectic order. The current?–?voltage characteristic of the device has a very sharp increase at low threshold voltage (5?V). A high carrier mobility of 1.8×10^‐2 was observed in the smectic phase of one of the compounds studied (e).     

Chemical reactivity within a smectic B liquid crystalline phase: A model of enzyme catalysis?

The rearrangement of allyl p-dimethylaminobenzenesulphonate (ASE) to form a zwitterionic product has already been recognized as an effective probe for the study of reactivity within the smectic B phase [4, 5, 19]. We have used deuterium NMR, linear dichroism and X-ray diffraction techniques to investigate the phase diagram of the ASE-OS35 reaction system. The partitioning of the reactant molecules between coexisting smectic, nematic and/or isotropic phases and the structural organization of the smectic catalytic host at different temperatures and reactant guest concentrations have been characterized. On the basis of these measurements, a model of ASE reactivity in smectic solvents has been developed. The reaction takes place provided that coexisting isotropic or nematic phases are present to act as a reservoir for the ASE reactant molecules prior to their entering the smectic phase; they then react and leave the smectic phase as a zwitterionic product. The analogy between this model of reactivity within smectic phases and the Michaelis-Menten enzyme processes is discussed. This relationship opens up the intriguing possibility of designing new experiments with which to investigate further liquid crystalline models of enzyme catalysis.     

A microscopic model considering the effect of molecular biaxiality on ferroelectric ordering of liquid crystalline smectic C* phases

On the basis of a mean-field approach, a microscopic model is presented to explain some ferroelectric properties of induced smectic C* phases of chiral dipolar guest molecules in an achiral smectic C host phase. The molecular biaxiality of the chiral dopants has been taken into account, resulting in a polar and quadrupolar ordering of the molecular short axes in the rotational distribution function of the guest molecules. This model explains the dependence of the magnitude and sign of the spontaneous polarization on the molecular structure of a series of cyclo-hexanone derivatives used as chiral dopants, as well as the effect of a local field at higher dopant concentrations.     

Synthesis and properties of new ferroelectric liquid crystalline compounds having a 1, 2-diphenylethane structure

Abstract

Chiral 1, 2-diphenylethane derivatives have been synthesized and found to form stable chiral Sc phases exhibiting ferroelectric properties. Comparison with diphenylacetylene derivatives revealed that flexibility of the bridging groups between two benzene nuclei strongly influences the stability of mesophases as well as transition temperatures.     

Electro-optic and dielectric properties of new binary ferroelectric and antiferroelectric liquid crystalline mixtures

Several new binary liquid crystalline mixtures have been designed and their properties were studied by complementary methods. It has been shown that even both pure components used for the mixture design possess the ferroelectric behaviour; the induced antiferroelectric smectic phase has been detected for one of the prepared mixtures. The phase diagram has been constructed and the existence of the antiferroelectric phase was confirmed by switching time and dielectric spectroscopy measurements. Some of the resulted mixtures possess very high values of the tilt angle that reaches close below 45° degrees at saturation. Values of spontaneous polarisation were found within 50–200 nC/cm² in dependence of the mixture’s composition. Due to specific properties, the obtained mixtures might be interesting for further design of multicomponent mixtures and formulation of the advanced nanocomposite systems.     

A tensor model of liquid crystalline polymers: application to basic disclination processes

One of the features of liquid crystalline polymers (LCPs) is their strong elastic anisotropy, which means they have unequal elastic constants. Elastic anisotropy plays a crucial role in the microstructure and macroscopic properties of LCPs. In this paper, the effect of unequal elastic constants on microstructure is investigated without an external field by using a deterministic tensorial approach. In this model, the evolution of the director field can be viewed as a process driven towards the state of zero elastic torque. A tensor expression of the elastic torque is used so that the nematic symmetry is automatically conserved. In simulations of bulk samples, disclination lines of strength half and escaped integer disclinations are observed. The distortion fields around the disclinations are found to depend on elastic anisotropy. If the twist constant is the lowest, as is the case for main chain liquid crystalline polymers, the disclination lines are predominantly of the twist type.     

Deformed helix ferroelectric liquid crystal display: A new electrooptic mode in ferroelectric chiral smectic C liquid crystals

Abstract

A new electrooptic mode of operation of ferroelectric chiral smectic C liquid crystal displays (LCDs) is proposed and demonstrated. The effect, which is called the deformed helical ferroelectric (DHF) effect, is based on the deformation of the helical structure by weak electric fields. In the unbiased device the smectic layers are arranged in the bookshelf geometry with the helix axis parallel to the electrodes [1]. Systems with a very small pitch (<1 μm) and a large tilt angle are especially well suited for this mode. The key characteristics of DHF-LCDs are: (a) low driving fields (1 V_p-pμm^?1 for maximum contrast); (b) grey scale which is approximately linear with the applied electric field; (c) easy alignment even for thick cells using standard wall-aligning methods; and (d) response times at room temperature of 300 μs.     

Molecular dynamics simulations of a liquid crystalline molecule in the smectic A and E phases and in vacuum

Molecular dynamics simulations are performed in this work at 393 and 323 K for a mesogenic molecule ( R )-1-methylheptyl 4\[4-(2-allyloxyethoxy)biphenyl-4-carbonyloxy]benzoate in the simulated smectics A and E, respectively, and in a vacuum at 300 K, for a period of 1.0ns. The trajectories obtained from molecular dynamics simulations allow us to investigate the dynamical behaviour of this mesogenic molecule in the simulated smectic phases. This dynamical behaviour of a single molecule is presented using the distributions of dihedral angles and rotational diffusion around the C-axis defined by the simulated cells. Simulation results indicate that, except for the bonds near the end of the spacer segment, the dihedral angles all exhibit a single Gaussian-like distribution in the smectic A and E phases. Fluctuations of a dihedral angle about its mean value are more restricted in the smectics A and E than in those simulated in a vacuum. The average value of the fluctuations of the dihedral angles at the bonds in the spacer is found to be about 2 fold larger than that of fluctuations in the tail of the same molecule in the smectic A and E phases. In the smectic A phase, the distribution of orientations of a molecule about its long axis in a 36 molecule cell in which the outer molecules are fixed is found to have three distinct peaks. This result shows that the orientational fluctuations of single molecules are limited by confinement due to neighbouring molecules, i.e. that the layers have short-range structural correlations. The orientational distributions show larger fluctuations at the ends of the molecules.     

Mesomorphic and structural properties of liquid crystalline side-chain polymethacrylates: from smectic C* to columnar phases

The chiral methacrylate monomers with photosensitive azobenzene group possessing the orthogonal smectic A* and tilted smectic C* (Sm-C*) phases have been synthesised and characterised. The monomers have been used as functional side chains for the design of corresponding polymethacrylates. X-ray diffraction has been applied to elucidate the structure and phase behaviour of liquid-crystalline side-chain polymethacrylates with azobenzene-containing central core, chiral fragments and aliphatic spacers and tails of different length. X-ray patterns of polymethacrylates oriented fibres impose the tilted Sm-C* order as a basic structure of these materials. This is complemented by a regular pattern of small-angle diffuse spots, which implies complex positional order on the local scale and serves as a precursor for the formation of a columnar phase. The increase of the total length of the aliphatic tail and spacer of the side-chain fragments leads to formation of the tilted columnar phase (Col_tilt*) with two-dimensional monoclinic lattice. For the polymer containing 10 methylene units in both, spacer and aliphatic tail, the Col_tilt* precedes the formation of the Sm-C* phase. The observed structural changes are explained as due to coupling between the smectic ordering of the mesogenic side groups and the polymer backbone conformation.     

A hydrogel‐forming liquid crystalline elastomer exhibiting soft shape memory

Research in the field of liquid crystalline polymers has recently witnessed the introduction of liquid crystalline hydrogels. Here, we report the synthesis and characterization of a new liquid crystalline network featuring elastomeric softness, water‐swelling and shape memory characteristics. By comparing with a nonmesogenic network prepared using the same procedure, we reveal structure–property relationships of the liquid crystalline and crystalline polymer networks. Wide angle and small angle X‐ray scattering studies were used to examine the liquid crystalline ordering in both dry and hydrated states. Such ordering was found to be related to the observed shape memory and actuation (two‐way shape memory) properties and these phenomena are highlighted with demonstrations of shape change in response to heat and water stimuli. This study provides insight into the mechanisms affecting the shape evolution of water activated anisotropic liquid crystalline hydrogels and enables the future design of materials or devices for a variety of applications such as biomaterials interacting with body fluids in a hydrated state. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 38–52     

Effect of cholesteric liquid crystalline elastomer with binaphthalene crosslinkings on thermal and optical properties of a liquid crystal that show smectic A‐cholesteric phase transition

A side‐chain polysiloxane cholesteric liquid crystalline elastomer (ChLCE) with binaphthalene derivate as crosslinkings and cholesterol derivate as liquid crystalline monomers was designed and synthesized. A binaphthyl chiral dopant (CD) was synthesized as well. The chemical structures and liquid crystalline properties of the ChLCE and the CD were characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, element analyses, differential scanning calorimetry and polarizing optical microscopy measurements. The helical twisting power of the ChLCE exhibited a turning point with changing temperature and was smaller than that of the CD. In addition, the effect of the ChLCE on phase transition temperatures and thermal‐optical properties of a liquid crystal that show smectic A (SmA)‐cholesteric (Ch) phase transition was studied. Worthily, the testing of the reflection wavelength with changing temperature suggested that the adding of the ChLCE in liquid crystals that show SmA‐Ch phase transition can expedite their SmA‐Ch transition. In addition, the network structure of the ChLCE may play a significant role in the accelerating of the transition. These properties provided theoretical and experimental foundations for applying ChLCE in thermally sensitive liquid crystal devices requiring fast response, such as thermally controllable windows, materials and displays. Copyright © 2012 John Wiley & Sons, Ltd.     

Dimeric liquid crystalline compounds having a central malonic acid moiety: effect of the length of the spacers and terminal chains

We have studied the liquid crystalline properties of two new series of dimeric compounds consisting of a central malonic acid moiety, polymethylene spacers, and Schiff's base mesogens. In the first series we changed the length of the spacers with the terminal chain fixed as the butoxy group; in the second series we changed the length of the terminal alkyl or alkoxy groups while keeping the spacers fixed as decamethylene groups. In the first series, as the length of the spacer increased, the tendency to form smectic phases grew. In the second series, changing the alkyl terminal chain to the alkoxy terminal group raised the melting and isotropization temperatures. Increasing the length of the terminal group diminished the temperature range for the higher temperature smectic phase. The smectic phases are assigned to be smectic A and crystal smectic E phases.     

侧基甲壳效应和甲壳型液晶高分子

侧链液晶高分子体系里,液晶基元可以通过尾接或腰接的方式与主链相连.一般认为,在液晶基元与主链间插入一段长度合适的＂柔性间隔基＂可有效实现主、侧链间的动力学去偶合,从而有利于侧基液晶基元之间的有序排列.作为一类特殊的腰接型侧链液晶高分子,甲壳型液晶高分子中体积较大的侧基（如棒状液晶基元）通过非常短的间隔基或仅通过一个碳-碳键直接横挂至主链上,这导致了强烈的甲壳效应,使得主链被迫伸展.因此,可从与＂柔性间隔基＂完全不同的角度出发,充分利用主链和侧基间的偶合作用,设计甲壳型液晶高分子.本文综述了腰接型侧链液晶高分子中的侧基甲壳效应、甲壳型液晶高分子中由主链与侧基相互作用所导致的特殊构象以及液晶相结构.研究表明,侧基甲壳效应在调控甲壳型液晶高分子的形状、尺寸以及螺旋结构等方面有重要作用.甲壳型液晶高分子可作为刚-柔嵌段共聚物的刚性链段,也可作为主/侧链结合型液晶高分子的主链部分参与到多层次分级超分子有序结构的构筑之中.     

A new series of nematic and smectic liquid crystals with negative dielectric anisotropy: the effect of terminal chain substitution on thermal and electro-optical properties

Two alkyl (1b and 1c) and four fluoroalkyl derivatives (1d-1f) of 4-arylbutyric acid (1c, 1d and 1e) and 4-arylbutanol (1b, 1f and 1g) [aryl = 2',3'-difluoro-4'-(2-(E-4-pentylcyclohexyl)ethyl)-biphenyl-1-yl] were prepared and investigated in the pure form as nematic materials (1b and 1c) and as additives to a ferroelectric liquid crystal (FLC) host (1d-1f). A comparison of 1b and 1c with the decyl analogue 1a demonstrates the effect of terminal chain modification on thermal and electro-optical properties. The substitution of the -CH₂O- (1b) or -COO- (1c) for -CH₂CH₂- in 1a destabilized the N and SmA phases or completely eliminated the smectic behaviour (1c). Dielectric analysis revealed that the chain modification increased the negative Δε, reduced elastic constant K ₁₁ and moderately decreased rotational viscosity γ₁. The temperature dependence of the key electro-optical parameters was analysed for ester 2, the methyl analogue of 1c, which exhibits a 45 K wide N phase. All four fluoroalkyl derivatives 1d-1f showed enantiotropic SmA phases and 1e also exhibited a monotropic SmC phase. Solutions of 1d-1f in a FLC host (0.2 mmol g^-1) increased the tilt angle Θ (up to 45° for 1g), reduced rotational viscosity γ₁ and the risetime τ. The most dramatic changes were observed for 1g, which contains 15 fluorine atoms.     

新型噻二唑类液晶的合成与研究

合成了以酰胺键为中心桥键的三芳环1,3,4-噻二环系共8个新化合物。液晶性质测试证明它们均为具有高相变温度和宽相变范围的稳定的液晶化合物。     

Thermal and ionic‐conductive behaviors of liquid crystalline polymers with alkali metal salt

In order to investigate the relationship between ionic conductivity and liquid crystallinity, we prepared the main‐chain type polyester having 1,4‐bisstyrylbenzene units and ethyleneoxide chain in the repeating unit. The main‐chain type polyester with lithium salt at the ratio of 0.04 per polymer repeating unit exhibited a smectic phase. However, the polyester with lithium salt (0.11) showed a nematic phase. The ionic conductivity of the polyester with lithium salt increased with increasing lithium salt concentration. The trans‐type polyester exhibited a liquid crystalline phase, while the cis‐type polyester did not show any mesophase. We found that the ionic conductivity of the trans‐type polyester with lithium salt (0.11) was larger than that of the cis‐type polyester with lithium salt (0.11). However, a liquid crystalline phase was found in the side‐chain type polyether with alkoxy chain length of below 12. A smectic phase was induced for the non‐mesomorphic polyethers with lithium salt. The layer spacing of the smectic A phase for the non‐mesomorphic polyether with lithium salt decreased from 55 to 41 Å with increasing temperature. The ionic conductivity of the polyether with lithium salt increased with decreasing the layer spacing. Copyright © 2001 John Wiley & Sons, Ltd.     

The effect of chiral doping in achiral smectic liquid crystals on the de Vries characteristics: smectic layer thickness,electro-optics and birefringence

An addition of chiral dopant to two achiral smectic liquid crystals from a homologous series, by varying weight percentages with known low values of layer shrinkage, leads to chiral smectic-C* phase with a finite value of the spontaneous polarisation. The electro-optical response arising from changes in the induced apparent tilt angle brought about by a weak electric field in the SmA* phase gives rise to power law dependency on the reduced temperature. The critical exponent γ of the power law depends on the dopant concentration but its value is found to be greater than the typical value of 1.32. This implies that the short-range correlation extends from two dimensions to three dimensions in these materials in the SmA phase. The layer thickness of smectic layers in the guest–host system remains unaltered up to the 15 wt % addition of the chiral dopant to two achiral smectics. The system thus retains the low layer shrinkage of the achiral smectic as evidenced by measurements of the layer thickness from X-ray scattering and thickness measurements from optical interferometry. Results on the optical birefringence and the apparent tilt angle lead us to the conclusion of having successfully obtained chiral smectic materials for devices with de Vries characteristics by chiral doping.     

A new series of siloxane liquid crystalline dimers exhibiting the antiferroelectric phase

In this paper, we report the study of a new series of symmetric chiral liquid crystalline siloxane dimers, their related monomers, and two of those monomers with heptamethyltrisiloxane attached. All the dimers coupled with a trisiloxane show the SmC_A phase, which in several cases has a large tilt angle greater than 40° over a wide temperature range, as well as high spontaneous polarisation in the field‐induced ferroelectric state. Spacer lengths of 3–6 and 11 carbons between the siloxane central unit and the mesogenic cores were used. Monomers with 3–6 carbons in the spacer showed only orthogonal phases while the monomer with an 11‐carbon spacer, as well as the monomers with siloxane attached, have a high tilt angle ferroelectric phase. The materials were characterized by means of DSC, NMR, X‐ray diffraction, electro‐optical methods (tilt angle and texture characterization) and polarization measurements.