Optical behaviour of photoimageable cholesteric liquid crystal cells with various novel chiral compounds

In theory, both polarity and steric hindrance are basic factors which affect molecular interactions. To investigate the optical properties and steric structures of chiral compounds having different chiral moieties which affect the wavelength of light reflection in liquid crystal (LC) cells, a series of novel chiral compounds and azobenzene derivatives were synthesized. The liquid crystalline phases of the compounds were identified using small angle X‐ray diffraction, differential scanning calorimetry and polarizing optical microscopy. Cholesteric LC cells with various synthesized chiral dopants which selectively reflect visible light were first prepared, the photochemical switching behaviour of colours was then investigated, with special reference to the change in transmittance in cholesteric LC cells containing an azobenzene derivative as a photoisomerizable guest molecule. Reversible isomerization of azobenzene molecules occurred in the cholesteric systems, resulting in a depression of T _ChI and a shift of the selectively reflected wavelength. We discuss the photochemically driven change in the helical pitch of the cholesteric LCs with respect to structural effects involving the chiral moieties. Molecular interactions caused by the added dopants, reliability and stability of the photoisomerization, and UV irradiation effects on the cholesteric LC cells were also investigated. A real image was recorded through a mask on a cholesteric LC cell fabricated in this investigation.     

Photochemical tuning capability of cholesteric liquid crystal cells containing chiral dopants end capped with menthyl groups

In order to investigate the photochemical tuning capability of chiral monomers and polymers containing end-capped menthyl groups, a new series of chiral dopants was synthesized and added to commercially available nematic liquid crystals to induce cholesteric liquid crystal (LC) phases. The addition of chiral dopants with azo structure led to phototunability of the reflection colour of the LC cells. Photochromic variation of the LC cells due to photoisomerization of the azo compound was investigated. After photopolymerization of the monomers inside the cholesteric LC cells, the centre wavelength of the reflected band of the incident light was found to be fixed and the reflected bandwidth was broadened, resulting in a red shift. A schematic representation of both the photoisomerization of the azo dopants and its effect on variation of twisting pitches is proposed. Real image recording was performed using 365 nm UV through a mask with text. The top and side views of the morphological network structures of a fabricated cholesteric LC cell were investigated using scanning electron microscopy. The results of this investigation demonstrated that RGB reflected colours of LC cells can easily be achieved through the addition of the menthyl-containing synthesized chiral compounds to nematic LCs. The addition of synthesized AzoM helped further in recording the patterns onto cholesteric LC films using 365 nm UV exposure.     

Photochemical tuning capability of cholesteric liquid crystal cells containing chiral dopants end capped with menthyl groups

In order to investigate the photochemical tuning capability of chiral monomers and polymers containing end‐capped menthyl groups, a new series of chiral dopants was synthesized and added to commercially available nematic liquid crystals to induce cholesteric liquid crystal (LC) phases. The addition of chiral dopants with azo structure led to phototunability of the reflection colour of the LC cells. Photochromic variation of the LC cells due to photoisomerization of the azo compound was investigated. After photopolymerization of the monomers inside the cholesteric LC cells, the centre wavelength of the reflected band of the incident light was found to be fixed and the reflected bandwidth was broadened, resulting in a red shift. A schematic representation of both the photoisomerization of the azo dopants and its effect on variation of twisting pitches is proposed. Real image recording was performed using 365 nm UV through a mask with text. The top and side views of the morphological network structures of a fabricated cholesteric LC cell were investigated using scanning electron microscopy. The results of this investigation demonstrated that RGB reflected colours of LC cells can easily be achieved through the addition of the menthyl‐containing synthesized chiral compounds to nematic LCs. The addition of synthesized AzoM helped further in recording the patterns onto cholesteric LC films using 365 nm UV exposure.     

Photosensitive cholesteric polymers with azobenzene-containing chiral groups and mixtures of cholesteric copolymer with chiral-photochromic dopants

New chiral photochromic cholesteric comb-shaped acrylic copolymers and low molecular mass dopants containing azobenzene photosensitive fragments and chiral groups based on menthol and menthone were synthesized. For the copolymers and their mixtures with low molecular mass dopants, the phase behaviour and optical properties were studied. Under irradiation with UV and visible light, the untwisting of cholesteric helix takes place, and the selective light reflection maximum is shifted to the long wavelength spectral region. This shift is related to the E-Z isomerization of the azobenzene chiral groups. For the copolymers and mixtures of the cholesteric polymer with the menthyl-containing dopant, this process is thermally reversible. The specific features of the kinetics of the forward and the reverse thermal processes were characterized. It was demonstrated, that the copolymers and mixtures of the cholesteric copolymer with the menthyl-containing dopant may be used for coloured reversible recording of optical information. For such materials, their resistance with respect to the repeated 'recording-erasing' cycles was tested, and the fatigue resistance was shown to be rather high.     

Photosensitive cholesteric polymers with azobenzene-containing chiral groups and mixtures of cholesteric copolymer with chiral-photochromic dopants

New chiral photochromic cholesteric comb-shaped acrylic copolymers and low molecular mass dopants containing azobenzene photosensitive fragments and chiral groups based on menthol and menthone were synthesized. For the copolymers and their mixtures with low molecular mass dopants, the phase behaviour and optical properties were studied. Under irradiation with UV and visible light, the untwisting of cholesteric helix takes place, and the selective light reflection maximum is shifted to the long wavelength spectral region. This shift is related to the E-Z isomerization of the azobenzene chiral groups. For the copolymers and mixtures of the cholesteric polymer with the menthyl-containing dopant, this process is thermally reversible. The specific features of the kinetics of the forward and the reverse thermal processes were characterized. It was demonstrated, that the copolymers and mixtures of the cholesteric copolymer with the menthyl-containing dopant may be used for coloured reversible recording of optical information. For such materials, their resistance with respect to the repeated 'recording-erasing' cycles was tested, and the fatigue resistance was shown to be rather high.     

Reversible photo-regulation of the properties of liquid crystals doped with photochromic compounds

Photochromic reactions in liquid crystals induce re-alignments of the host molecules, accompanied by changes in the optical properties and various other properties of the materials. Since the first report by Sackmann in 1971, various combinations of photochromic compounds and liquid crystals have been studied to elicit the reversible photo-regulated changes of various properties. In this report we review the advances of this field during the past 5 years, which include the creation of mechanical functions, the regulation of novel optical properties, cholesteric liquid crystals doped with azobenzene compounds in high concentrations, the regulation of ferroelectric liquid crystals, the induction of chirality by circularly polarized light, photoresponsive chiral dopants, and the photo-regulation of the oscillation wavelength of mirrorless lasers.     

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.     

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.     

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.     

Synthesis and characterization of chiral compounds containing cationic groups as chiral dopants in liquid crystals

Novel chiral molecules containing cationic groups, (N-[4-triethylammoniomethyl]-benzoyl ester)-ethyl lactate chloride and bi-(N-[4-triethylammoniomethyl]-benzoyl ester)-isosorbide chloride, were designed and synthesized. Chemical structures of the molecules were characterized by elemental analysis, FT-IR, and (1)H NMR. The photochemical properties of the chiral compounds and their textures in nematic liquid crystals (LCs) were investigated by optical rotation, circular dichroism (CD), and polarizing optical microscopy (POM). The novel chiral molecules exhibited good optical activity. The chiral compound based on a L-ethyl lactate chiral center had a left-handed configuration. The chiral compound based on an isosorbide chiral center had a right-handed configuration. The cationic polar groups did not affect the direction of optical rotation, but could effluence the molar rotation of chiral compounds. The mixtures with dopants showed oily streak textures. Doping of a nematic phase liquid crystal with the chiral molecules converted it to the cholesteric phase.     

Photochemical tuning of the helical structure of cholesteric liquid crystals by photoisomerization of chiral azobenzenes, and their structural effects

Several chiral azobenzene compounds having different chiral substituents were synthesized. A cholesteric phase was induced by mixing each chiral azobenzene compound with a host non-chiral nematic liquid crystal (E44). The helical twisting power (HTP) as well as the change in HTP by trans-cis photoisomerization of the chiral azobenzene compound was dependent on the structure of the chiral substituents. A compensated nematic phase was induced by combination of E44, a chiral azobenzene compound and a non-photochromic chiral compound. Reversible switching between the compensated nematic phase and cholesteric phase was brought about by trans-cis photoisomerization of the chiral azobenzene compound in the liquid crystalline systems. An azobenzene compound substituted with a menthyl group showed the highest efficiency as the trigger for the switching; this efficiency was related to the compactness of the chiral group substituted within the azobenzene core moiety.     

The influence of molecular structure on helical twisting power of chiral azobenzene compounds

Photochromic chiral azobenzene compounds with different molecular structures were synthesized, and a cholesteric phase was induced by mixing each chiral azobenzene compound with a non-photochromic chiral compound in a host nematic liquid crystal, E44. Helical pitch and, thus, helical twisting powers (HTP) of the chiral azobenzene compounds and the non-photochromic chiral compound were determined by Cano's wedge method. Molecular structures of the chiral azobenzene compounds were predicted by means of determining their molecular aspect ratio (L/D) with semiempirical molecular calculations (MOPAC at PM3 level). The effects of molecular structure on HTP of the chiral azobenzene compounds are studied in detail. Molecular structures of chiral azobenzene compounds significantly influence their HTPs.     

Thermal tuning band gap in cholesteric liquid crystals

The phase of a liquid crystal (LC) changing from a nematic phase to a cholesteric (Ch) mesophase is achieved by adding different ratios of chiral dopants S811. By studying the transmission spectrum, we are able to measure the helical pitch in cholesteric phase. The pitch in the mixtures of nematic E7 and chiral dopants S811 as a function of the concentration of the dopant and temperature is investigated. The sensitivity of the selective reflection notch of the cholesteric phase to the thermal tuning depends strongly on the ratios of the chiral dopants. It reveals that the influence of temperature is more profound for those cholesteric liquid crystals (CLCs) which exhibit smectic A (SmA) at lower temperatures. When fitted using Keating's formula, the helical pitch calculated from our experimental results lies on the predicted curve. Optimised ratios of the mixture CLCs for the optimised reflection band with the specified wavelength ranging from 467 nm to 2123 nm are suggested.     

Light-induced structural changes in chiral liquid crystals

Novel light-sensitive chiral dopants are studied as a light-sensitive component in chiral liquid crystals which may be used in tunable optical devices. Light-induced cis-trans- isomerization of chiral dopants results in changes of helical twisting power which translates into variations of helical pitch. Due to the light absorption in the liquid crystal cell the pitch variation is non-uniform across the cell, which leads, at first, to a deformation of cholesteric layers, and then to the formation of cholesteric bubbles. The sequence of structural changes has a distinct visual pattern and occurs at the surface close to the UV light source. Small deformations of cholesteric layers and bubbles are unstable and disappear after removing UV irradiation. The increasing size of the cholesteric bubbles results in better stability; large bubbles do not disappear after removing UV light. A theoretical model is suggested to describe the undulations of cholesteric layers.     

Photocontrolled manipulation of a microscale object: a rotational or translational mechanism

In this paper the photocontrolled manipulation of solid materials on the surface of a liquid crystalline thin film is described. Three different types of films namely cholesteric liquid crystal (ChLC), compensated nematic liquid crystal (NLC) and nematic LC were used. The rotational and translational manipulation of the microscale solid object was induced by irradiation of light and mode of manipulation (either translational or rotational) was changed by changing the isomer of the azobenzene compound used to make the film. Rotational motion of the object was observed on the ChLC and compensated NLC films containing chirally pure azobenzene compound. The direction of rotational motion was controlled either by changing the optical isomer of the chiral azobenzene or by changing the irradiating light (from ultraviolet to visible). When racemic mixture of the chiral azobenzene compound was used, a translational motion of the object was observed. Even though the direction of the translational motion can be controlled by controlling irradiation position, more facile and precise manipulation of the objects was possible by spatially controlled irradiation of Ar(+) laser and diode UV laser.     

Dynamic photoswitching of helical inversion in liquid crystals containing photoresponsive axially chiral dopants

Chirality switching is intriguing for the dynamic control of the electronic and optical properties in nanoscale materials. The ability to photochemically switch the chirality in liquid crystals (LCs) is especially attractive given their potential applications in electro-optic displays, optical data storage, and the asymmetric synthesis of organic molecules and polymers. Here, we present a dynamic photoswitching of the helical inversion in chiral nematic LCs (N*-LCs) that contain photoresponsive axially chiral dopants. Novel photoresponsive chiral dithienylethene derivatives bearing two axially chiral binaphthyl moieties are synthesized. The dihedral angle of the binaphthyl rings changes via the photoisomerization between the open and closed forms of the dithienylethene moiety. The N*-LCs induced by the dithienylethene derivatives that are used as chiral dopants exhibit reversible photoswitching behaviors, including a helical inversion in the N*-LC and a phase transition between the N*-LC and the nematic LC. The present compounds are the first chiral dopants that induce a helical inversion in N*-LC via the photoisomerization between open and closed forms of the dithienylethene moiety.     

Photochemically reversible and thermally stable axially chiral diarylethene switches

A series of dithienylcyclopentenes containing axially chiral 1,1'-binaphthyl units were successfully synthesized by a Suzuki-Miyaura protocol. All these compounds exhibited photochemically reversible isomerization with thermal stability in both organic solvent and a liquid crystal (LC) host. When doping into an achiral LC host, some of them exhibited very high helical twisting powers. Reversible reflection wavelength tuning in the visible region and LC phase switching between nematic and cholesteric upon light irradiation were demonstrated.     

Photoinduced reorientation processes in thin films of photochromic LC polymers on substrates with a photocontrollable command surface

Orientation and reorientation processes that occur in nematic and cholesteric LC polymer systems under irradiation with plane-polarized light are studied. A copolyacrylate containing phenyl benzoate and azobenzene side groups is synthesized as a nematic polymer; the cholesteric mixture is prepared via doping of the nematic copolymer with the chiral dopant, the derivative of D-isosorbide. Thin layers of the azobenzene-containing photoorientant SD-1 are first used as orienting substrates for polymer liquid crystals. Thin layers of the copolymer and of the mixture are spin-coated on the substrate after irradiation of the photoorientant layer with polarized light. It is shown that after annealing phenyl benzoate and azobenzene side groups of the nematic copolymer orient strictly along the direction of orientation of surface molecules, whereas in the case of the cholesteric mixture, a partial formation of the helical structure is observed. It is demonstrated that all the systems under examination can experience the repeated cyclic reorientation of the cooperative type under irradiation and subsequent annealing of the films.     

Influence of a Change in Helical Twisting Power of Photoresponsive Chiral Dopants on Rotational Manipulation of Micro‐Objects on the Surface of Chiral Nematic Liquid Crystalline Films

Herein we report a group of five planar chiral molecules as photon‐mode chiral switches for the reversible control of the self‐assembled superstructures of doped chiral nematic liquid crystals. The chiral switches are composed of an asymmetrically substituted aromatic moiety and a photoisomerizing azobenzene unit connected in a cyclic manner through methylene spacers of varying lengths. All the molecules show conformational restriction in the rotation of the asymmetrically substituted aromatic moiety in both the E and Z states of the azobenzene units resulting in planar chirality with separable enantiomers. Our newly synthesized compounds in pure enantiomeric form show high helical twisting power (HTP) in addition to an improved change in HTP between the E and Z states. The molecule with a diphenylnaphthalene unit shows the highest ever known initial helical twisting power among chiral dopants with planar chirality. In addition to the reversible tuning of reflection colors, we employed the enantiomers of these five compounds in combination with four nematic liquid crystalline hosts to study their properties as molecular machines; the change in HTP of the chiral dopant upon photoisomerization induces rotation of the texture of the liquid crystal surfaces. Importantly, this study has revealed a linear dependence of the ratio of the difference between HTPs before and after irradiation against the absolute value of the initial HTP, not the absolute value of the change in helical twisting power between two states, on the angle of rotation of micro‐objects on chiral nematic liquid crystalline films. This study has also revealed that a change in irradiation intensity does not affect the maximum angle of rotation, but it does affect the speed of rotational reorganization of the cholesteric helix.     

Synthesis and spatial structure of new chiral dopants from allobetuline series for cholesteric liquid-crystal compositions

Structural Chemistry - New series of chiral dopants for cholesteric liquid-crystal compositions were synthesized on the base of 2-substituted allobetuline derivatives, and their steric structure...