Effect of specific rotation of chiral dopant and polymerization temperature on reflectance properties of polymer stabilized cholesteric liquid crystal cells

A series of polymer stabilized cholesteric liquid crystal (PSCLC) cells were prepared by photo‐polymerization of a cholesteric liquid crystal (Ch‐LC) mixture containing a nonreactive LC, a nematic diacrylate and a novel cholesteryl monomer. The influence of the specific rotation and concentration of the chiral dopants, and the polymerization temperature on reflection properties was investigated. The results demonstrate that the reflection band was broadened after polymerization for all the systems both left‐handed S811 and right‐handed R1011 as the chiral dopant, which is speculated to be a result of an inhomogeneous consumption of the chiral monomer within the system. Additionally, the polymer temperature plays an integral role in the observed reflection spectra, and at optimum polymerization temperature the broadband reflection effect becomes much more pronounced. Scanning electron microscopy (SEM) was used to examine the role of microscopic changes of the polymer network induced by polymerization temperature. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1562–1570, 2008     

Influence of helical twisting power on the photoswitching behavior of chiral azobenzene compounds: applications to high-performance switching devices

Five photochromic chiral azobenzene compounds and one nonphotochromic chiral compound were synthesized and characterized by IR, 1H NMR spectroscopy, and elemental analysis. Cholesteric liquid crystalline phases were induced by mixing of the nonphotochromic chiral compound and one of the photochromic chiral azobenzene compounds in a host nematic liquid crystal (E44). The helical pitch of the induced cholesteric phase was determined by Cano's wedge method and the helical twisting power (HTP) of each sample was thus determined. The helical twisting powers of azobenzene compounds were decreased upon UV irradiation, due to trans-->cis photoisomerization of azobenzene molecules. Among the azobenzene compounds synthesized in our study, Azo-5, with isomannide (radical) as chiral photochromic dopant, showed the highest HTP and contrast ratio (Tmax/Tmin). Photoswitching between compensated nematic phase and cholesteric phase was achieved through reversible trans<-->cis photoisomerization of the chiral azobenzene molecules through irradiation with UV and visible light, respectively. Transmission rates (contrast ratios) increased with decreasing helical pitch length in the induced cholesteric phase. The influence of helical twisting power on the photoswitching behavior of chiral azobenzene compounds is discussed in detail.     

Short wavelength light reflecting films from side‐chain liquid crystal homopolymers with chiral spacers

A series of acrylate monomers with alkoxy tails of varying lengths are synthesised and polymerised. The butoxy analogue had a stable enantiotropic cholesteric liquid crystalline phase which formed a grandjean texture when prepared as a thin film between glass slides. The polymer was mixed with a low molar mass nematic liquid crystal in various proportions and the pitch of the chiral nematic phases were determined using a cano‐wedge cell technique. The polymer prepared from (S)‐2‐(4‐butoxyphenyl‐4′‐benzoyloxy)‐1‐methyl ethyl acrylate had a pitch length of 113 nm which indicates that the polymer film could be employed in optical devices requiring selective reflection of light with short wavelengths in the region of 170 nm. Copyright © 2001 John Wiley & Sons, Ltd.     

Bis-chelated imine-alkoxytitanium complexes: novel chiral dopants with high helical twisting power in liquid crystals

Enantiomerically and diastereomerically pure bis-chelated imine-alkoxytitanium complexes 6 and 7 have been synthesized and used as chiral dopants for converting nematic into cholesteric phases. The dopants were tested in mainly commercially available nematic liquid crystalline compounds or mixtures: LC1 (BASF), ZLI-1695 and ZLI-1840 (Merck), as well as N-(4-methoxybenzylidene)-4'-butylaniline (MBBA). The values of the helical twisting power (HTP) were determined by the Grandjean-Cano method. Exceptionally high helical twisting powers were obtained. Thus, the titanium complex 6 h displayed a HTP value of 740 microm(-1) in MBBA, the highest HTP value reported. The helical twisting power has been found to depend strongly on the structure of the nematic phase and the substitution pattern of the chiral ligand in the titanium complexes 6 and 7. Crystal structure analysis of 6 f confirmed the A,R,R configuration of the metal complex. The chiral imine ligands 4 and 5 were derived from the regioisomeric amino alcohols 1 and 2.     

Tuning helical twisting power and photoisomerisation kinetics of axially chiral cyclic azobenzene dopants in cholesteric liquid crystals

ABSTRACT

Significant attention has been paid to improve the helical twisting power (β) and Δβ between the two different isomers of axially chiral azobenzene dopants in cholesteric liquid crystals (CLCs); however, the correlations between the vales (β and Δβ) with the molecular structures as well as photoisomerisation kinetics are far from clear. In this study, a series of binaphthyl-azobenzene cyclic dopants R1–R3 with different lengths of alkoxy chain was synthesised, which exhibited photochemically reversible trans–cis isomerisation in both organic solvents and liquid crystal hosts. When doping into a nematic liquid crystal, dopant R2 with one linking alkoxy group showed the highest values of β and Δβ. The results revealed that the β value was related to the dihedral angle between two naphthyl planes and the miscibility between the dopants and the host molecule. Moreover, Δβ was also depended on the photoisomerisation quantum yields. With increasing length of alkoxyl chain, the photoisomerisation rate constant of dopants increased upon ultraviolet irradiation and decreased for the reverse process upon visible light irradiation either in isotropic acetonitrile or in CLCs. These results enable the precise tuning of the pitch and selective reflection wavelength of CLCs.     

Thermally bandwidth-controllable reflective liquid crystal film from rupture and self-assembly of hydrogen bonds

A cholesteric liquid crystal (Ch-LC) composite containing a hydrogen bond (H-bond) chiral dopant (HCD) was prepared and filled into a planar treated cell. When the cell was heated, the selective reflection of the cell exhibited an unusual red shift. One of the reasonable mechanisms was that the H-bonds of HCD ruptured when the temperature was high, and the HCD split into two new chiral dopants (CDs), which made the whole helical twisting power (HTP) value in the composite changed a lot, thus the pitch length of the composite changed. On the basis of this mechanism, when the composite was polymerised at the temperature of H-bonds of HCD ruptured, the bandwidth of the obtained film can be tuned form wider to narrower reversibly by the rupture and self-assembly of H-bonds chiral molecules as the temperature changed, respectively.     

Double UV polymerisation with variable temperature-controllable selective reflection of polymer-stabilised liquid crystal (PSLC) composites

In this study, a method of preparing wide-band reflection cholesteric liquid crystals (CLCs) films by UV-radical polymerisation in combination with UV-cationic polymerisation is proposed. Because the helical twisting power (HTP) of the chiral dopant decreases with increasing temperature and the polymerisation rate of UV-initiated free radical polymerisation is faster than UV-initiated cationic polymerisation, by adjusting the temperature, broadband reflective films with non-uniform pitch distribution are obtained. The fractured surface of the polymer network of the broadband reflective films is observed by scanning electron microscopy (SEM), which reveals the presence of non-uniform pitch distribution. In addition, the influences of monomer concentration, UV light intensity and UV curing time on the consequent non-uniform pitch distribution have been studied.     

Discontinuous change in the helical pitch of cholesteric liquid crystals by photoisomerization of a chiral azobenzene molecule

This paper describes the discontinuous change in the helical pitch of a cholesteric liquid crystal (ChLC) by means of the photoisomerization of chiral azobenzene molecules under homogenous alignment conditions. A mixture of E44, R811 and Azo was prepared in the ratio 68/28/4, respectively. R811 and Azo have opposite twisting abilities such that they induce right- and left-handed helices, respectively when added to E44. The mixture was injected into a glass cell having a 2 or 5?µm cell gap, and treated for homogeneous molecular orientation. The wavelength of selective reflection from the ChLC was shifted to shorter wavelengths by the trans-cis photoisomerization of Azo. The change in the helical pitch was not only discontinuous, but also dependent on the cell thickness. The discontinuous change in the helical pitch was estimated to be almost the same as the half turn of the helical pitch in each cell gap, and was dependent on the number of helical half pitches in the glass cell. The homogeneous alignment condition affects the photochemical change in the helical structure of the ChLC system.     

基于胆甾相液晶的可调制光子晶体

将胆甾相液晶填充进胶体晶体内部空隙, 通过胆甾相液晶与胶体晶体的耦合, 构建了一种新型可调制液晶光子晶体. 填充于胶体晶体内部的胆甾相液晶织构呈现典型的手性近晶相(S)特征. 由于胆甾相液晶具有特定的选择性反射, 当胶体晶体的带隙处于胆甾相液晶的反射波长范围之内, 则随着温度的改变, 胶体晶体的带隙与胆甾相液晶的带隙同时发生蓝移. 在一定温度条件下, 胆甾相液晶的带隙将与胶体晶体的带隙发生耦合, 实现了光子晶体带隙在单峰与双峰之间的可逆切换.     

Lattice structure in liquid-crystal blue phase with various chiral concentrations

Lattice structures, including reflection lattice planes and lattice constant, of liquid-crystal blue phase I (BPI) are studied via the measurements on reflection spectrum and Kossel diagram as concentration of a chiral dopant is changed. Peaks of the reflection wavelength in BPI are mainly dominated by the lattice plane and the lattice constant, which are affected by the chiral concentration. In the chiral nematic state, as decreasing the chiral concentration the reflection peak will shift to a longer wavelength because the helical pitch linearly depends on the chiral concentration and becomes longer. However, this dependence of the chiral concentration and reflection wavelength is broken in the BPI. The reflection peak of BPI moves to a short wavelength when the chiral concentration is less due to the contraction of the lattice constant as well as helical pitch. Moreover, when the concentration of the chiral dopant increases over a certain value, a discontinuous shift in reflection peak occurs due to the production of the different lattice planes. It means that the relationship between the chiral concentration and the helical pitch in BPI is not the same as it in the chiral nematic phase and should be reconsidered.     

Mesomorphic properties of non-symmetric three-arm chenodeoxycholic acid-derived liquid crystals

Six three-arm star-shaped liquid crystals (LCs) based on chenodeoxycholic acid (CDCA), termed as G-BH, G-YD, G-FD, G-DJ, G-DZ and G-BX, respectively, have been synthesised. CDCA was used as the chiral core and the nematic side arm, 6-(4-(ethylbenzoyloxy) phenoxy)-6-oxohexanoic acid, was chosen to be introduced into the two hydroxyl of CDCA to synthesise cholesteric LC (CDCA2EA) and different structures were introduced into the carboxyl group of CDCA to prepare the three-arm star-shaped LCs. Chemical structures and LC properties of the six three-arm LCs were characterised by FTIR, ¹H-NMR, differential scanning calorimetry, thermogravimetric analysis, X-ray diffraction and polarised optical microscopy. G-BH and G-DJ displayed cholesteric phase with a long helical pitch; G-BX displayed nematic phase; and G-YD, G-FD and G-DZ displayed cholesteric phase on heating and on cooling. These results indicated that not only the chiral core CDCA but also the structures of the side arms played an important role in inducing the cholesteric phase of the CDCA-derived LCs. G-DZ displayed selective reflection, a wider ?λ and red shift on cooling.     

Derivatives of menthothiophene as chiral dopants for nematic liquid crystals

New chiral derivatives of thiophene fused with menthane, camphor or the 3R-3-methylcyclohexane ring were prepared and studied as chiral dopants in cholesteric liquid crystalline mixtures. The helical twisting power of the most effective compounds of this series, menthothiophenes, was strong enough to obtain selective reflection of visible light at 16 wt% concentration of the dopant in a non-chiral nematic host.     

Fabrication and optical characterization of imprinted broad‐band photonic films via multiple gradient UV photopolymerization

A structured broad‐band photonic film is fabricated by a novel method using multiple gradient UV‐induced polymerization in the presence of cholesteric liquid crystals (CLCs). Here, imprinting and broadening of the reflection band of chiral nematic mesophase cells are achieved via controlled UV polymerization. The intensity gradient of UV light is modified by the distance between UV lamp and sample cell, which affects the polymerization rate and leads to the formation of imprinted helical constructions with different pitches. In this study, a comparison of new design process with traditional UV polymerization process is carried out. After seven cycles of gradient UV polymerization, the imprinted photonic construction exhibited a broadened reflection band and Bragg reflection, even for isotropic materials. Because of this, the reflection bandwidth showed a 70% improvement. Additionally, two stacked imprinted cells with different pitches can reflect incident light with a bandwidth over the visible wavelength range of 480–680 nm. A broad‐band photonic polymer film can be imprinted using multiple gradient UV photopolymerization in the presence of CLCs. Forming a UV intensity gradient and controlling the rate of photopolymerization are key factors in broadening the reflection band. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 1427–1434     

Helical twisting properties of new chiral dopants with double (S)-1, 2-propanediol units for nematic liquid crystals

<正>A novel series of chiral dopants synthesized from(S)-1,2-propanediol and mesogenic carboxylic acids were characterized by FT-IR,~1H NMR,elemental analysis and their helical twisting properties were investigated by doping the chiral dopants into a nematic liquid crystal host(SLC-1717).The results show that,the helical pitch of N~*-LC mixture exhibited a terminal alkyl chain length dependence and the molecular twisting power β also exhibited a temperature dependence(increasing β with increasing temperature).     

Photo‐optical properties of polymer composites based on stretched porous polyethylene filled with photoactive cholesteric liquid crystal

A new type of polymer–liquid crystal composite with photovariable dichroism and birefringence is described. Porous stretched polyethylene films were used as polymer matrices. To induce a cholesteric phase in a commercial nematic host, a chiral photochromic dopant based on sorbide and cinnamic acid capable of E–Z isomerization under UV irradiation was used. A merocianine‐type substance was selected as a dichroic dye. Introduction of a dye‐doped cholesteric mixture with a helical pitch higher than ～300 nm to polymer film led to an almost complete transition from a cholesteric to an oriented nematic phase, as well as to an increase in birefringence and the appearance of dichroism. Decrease of the helical pitch by increasing in the chiral dopant concentration in the liquid crystal–polymer composite results in a reduction of the dichroism values. UV irradiation of polymer composite leading to an isomerization of the chiral dopant and helix untwisting induces a noticeable gradual growth of dichroism and birefringence. These new composites can be considered as promising materials for optical applications.     

Synthesis of chiral azobenzene-based compounds for use in the photochemical tuning of the helical structure of liquid crystals

We have synthesized azobenzene-based molecules containing either one or two chiral groups. A cholesteric phase can be induced by adding the chiral azobenzene compounds to a host nematic liquid crystal. We investigated the effects of the trans - cis photoisomerization of the chiral azobenzene compounds on the properties of the cholesteric phase, such as the helical pitch length. This can be increased or decreased by the photoisomerization of the chiral azobenzene compounds. We discuss the photochemically driven change in the helical pitch of the cholesteric phase with respect to structural effects involving the chiral groups.     

Chiral conflict. The effect of temperature on the helical sense of a polymer controlled by the competition between structurally different enantiomers: from dilute solution to the lyotropic liquid crystal state

Helical polymers appended with paired structurally different enantiomers, which have opposing helical sense preferences, yield a new kind of relationship between optical activity and temperature, and also reveal unusual details of the nature of chiral interactions. Consistent with a statistical physical theory developed for these experiments, the proportion of the competing chiral groups, determined by synthesis, fixes the compensation temperature at which the helical senses are equally populated. The lyotropic liquid crystal state formed by these polymers yields therefore a nematic state at any chosen temperature over a very wide range, with a cholesteric state arising with tightening pitch as temperature deviates from this point. Far from the nematic temperature, the pitch reaches the nanometer scale and therefore the reflection of visible light. Before crossing zero at the nematic temperature, the optical activity becomes so large that it may be observed with the unaided eye through crossed polarizers.     

Lehmann rotatory power: a new concept in cholesteric liquid crystals

By doping a nematic phase with a chiral molecule one obtains a cholesteric phase. Each chiral molecule is characterised by its helical twisting power (HTP) which is defined as HTP?=?q/(2πC) where q is the equilibrium pitch of the cholesteric phase and C the concentration (in wt%) of chiral molecules. In a similar way, we define the Lehmann rotatory power (LRP) as LRP?=?v/(2πC) where v is the thermomechanical Lehmann coefficient. By making compensated mixtures, we measured the HTP and the LRP of five chiral molecules (R811, S2011, CC, CB15 and CE4) dissolved in an eutectic mixture 8CB/8OCB. We found that, although these quantities were different, their ratio R?=?LRP/HTP changed little from one molecule to another. This result shows that the Lehmann effect is closely, but not completely, related to the twist of the phase.     

Synthesis of chiral azobenzene-based compounds for use in the photochemical tuning of the helical structure of liquid crystals

We have synthesized azobenzene-based molecules containing either one or two chiral groups. A cholesteric phase can be induced by adding the chiral azobenzene compounds to a host nematic liquid crystal. We investigated the effects of the trans-cis photoisomerization of the chiral azobenzene compounds on the properties of the cholesteric phase, such as the helical pitch length. This can be increased or decreased by the photoisomerization of the chiral azobenzene compounds. We discuss the photochemically driven change in the helical pitch of the cholesteric phase with respect to structural effects involving the chiral groups.     

Photo-optical properties of polymer composites based on stretched porous polyethylene filled with photoactive cholesteric liquid crystal

A new type of polymer-liquid crystal composite with photovariable dichroism and birefringence is described. Porous stretched polyethylene films were used as polymer matrices. To induce a cholesteric phase in a commercial nematic host, a chiral photochromic dopant based on sorbide and cinnamic acid capable of E-Z isomerization under UV irradiation was used. A merocianine-type substance was selected as a dichroic dye. Introduction of a dye-doped cholesteric mixture with a helical pitch higher than ∼300 nm to polymer film led to an almost complete transition from a cholesteric to an oriented nematic phase, as well as to an increase in birefringence and the appearance of dichroism. Decrease of the helical pitch by increasing in the chiral dopant concentration in the liquid crystal-polymer composite results in a reduction of the dichroism values. UV irradiation of polymer composite leading to an isomerization of the chiral dopant and helix untwisting induces a noticeable gradual growth of dichroism and birefringence. These new composites can be considered as promising materials for optical applications.