Non‐symmetric liquid crystal trimers

Four homologous series of non‐symmetric linear liquid crystalline trimers, the 4‐[(4‐{n‐[4‐(4‐methoxy‐phenylazo)phenoxy]alkyloxy}benzylidene)amino]benzoic acid 6‐[4‐(4‐methoxyphenylazo)phenoxy]hexyl esters, 4‐[(4‐{n‐[4‐(4‐cyanophenylazo)phenoxy]alkyloxy}benzylidene)amino]benzoic acid 6‐[4‐(4‐methoxyphenylazo)phenoxy]hexyl esters, 4‐[(4‐{n‐[4‐(4‐methoxyphenylazo)phenoxy]alkyloxy}benzylidene)amino]benzoic acid 6‐[4‐(4‐cyanophenylazo)phenoxy]hexyl esters and 4‐[(4‐{n‐[4‐(4‐cyanophenylazo)phenoxy]butoxy}benzylidene)amino]benzoic acid 6‐[4‐(4‐cyanophenylazo)phenoxy]hexyl esters, have been synthesized and characterized. In each series one spacer was held constant while the length of the second was varied from 3 to 12 methylene units. All these trimers were nematogenic and exhibited pronounced odd–even effects in both their clearing temperatures and associated entropies. Only two of the trimers exhibited a smectic phase, and specifically those containing two differing terminal mesogenic groups and an undecyl spacer. This strongly suggests the driving force for smectic phase formation is a combination of molecular shape and a specific interaction between unlike mesogenic units. The smectic phase has been assigned as a triply‐intercalated alternating smectic C phase, the first example of its kind.     

Non‐symmetric liquid crystal dimers containing the 4‐nitrobenzohydrazide group: synthesis and mesomorphic behaviour

The synthesis and mesomorphic behaviour are reported of a new series of dimers containing 4‐nitrobenzohydrazide and azobenzene groups as the mesogenic units. These non‐symmetric liquid crystal dimers are found to exhibit a monolayer smectic A phase (SmA₁). Lateral hydrogen bonding and strong dipole–dipole interactions are shown to be the major driving forces for the formation of the SmA₁ phase. The present study indicates that the intermolecular interactions and thus the mesophase morphology of the liquid crystal dimers can be controlled by the appropriate selection of the molecular fragments capable of forming H‐bonds.     

In situ photochemical conversion from cinnamoyl‐functionalized liquid‐crystalline monomers to liquid‐crystalline dimers

Liquid‐crystalline (LC) monomers, which were functionalized with a cinnamoyl group on their extremity, were synthesized and irradiated with UV light in their LC phases. In the presence of a triplet sensitizer, most LC monomers were converted into the corresponding dimers, which were produced by the cycloaddition reaction of the cinnamoyl group. The photodimerization reaction could proceed while the LC phases were maintained, because the dimers showed LC phases whose temperature ranges were wider than those of the corresponding monomers. A ¹H NMR study of the LC dimers indicated that the cyclobutane unit dominantly had an anti‐head‐to‐head configuration, that is, δ‐truxinate. As the LC monomers, which had a phenyl biphenyl‐4‐carboxylate moiety as a mesogen, showed smectic A phases and the corresponding dimers also exhibited smectic A phases, we estimated the smectic layer distances by X‐ray diffraction analysis and found that the dimers adopted the structure in which the two mesogens aligned laterally and existed in the same smectic layer in the LC phases.     

Synthesis and characterization of non‐symmetric chiral dimers

A new class of cholesterol‐based non‐symmetric dimers have been synthesized and characterized. They comprise O‐alkylated cinnamic acid and pro‐mesogenic cholesterol segments interlinked covalently through a methylene spacer varying in its length and parity. All the dimers and some of the key precursors have been studied for their phase behaviour. All the intermediates show mesomorphism. Importantly, the thermal properties of dimers are found to be critically dependent on the parity of the flexible spacer. The dimers with odd‐parity spacer display chiral nematic and/or twist grain boundary phases. In contrast, the dimers with even‐parity spacer are either crystalline or exhibit metastable chiral nematic and/or twist grain boundary phases with the exception of one compound for which two unknown mesophases have been observed. The odd–even effect was found to be indistinct for selective reflection wavelengths of the chiral nematic phase. For some dimers, a variation in the pitch of the chiral nematic phase as a function of temperature was observed. Cyclic voltammetry experiments revealed the electrochemical properties of a representative liquid crystal dimer.     

Crystal structure of a liquid crystal non‐symmetric dimer: cholesteryl 4‐[4‐(4‐n‐butylphenylethynyl)phenoxy]butanoate

The crystal structure of cholesteryl 4‐[4‐(4‐n‐butylphenylethynyl)phenoxy]butanoate [phase sequence: Cr 155°C (46.1?J?g^?1) SmA 186.8°C (1.5?J?g^?1) TGB‐N* 204.7 (6?J?g^?1) I] has been solved from single crystal X‐ray diffraction data. The compound crystallizes in the monoclinic space group P2₁ with unit cell parameters: a?=?13.129(2), b?=?9.3904(10), c?=?17.4121(8)?Å, β?=?92.790(7)°, Z?=?2. The structure has been solved by direct methods and refined to R?=?0.0606 for 3?250 observed reflections. The bond distances and angles are in good agreement with the corresponding values for compounds containing phenyl and cholesterol moieties. The phenyl rings A and B are planar. The dihedral angle between the least‐squares planes of the two phenyl rings is 28°. The cholesterol moiety has the usual structure: the C and E rings have chair conformations, and the D and F rings adopt half‐chair conformations. The molecules in the unit cell are arranged in an antiparallel manner. The crystal structure is stabilized by an intermolecular C–H…O contact of 2.989(10)?Å.     

Non‐symmetric bent‐core mesogens with one terminal vinyl group

Two series of non‐symmetric banana‐shaped compounds, both with one alkyl and one alkenyl terminal tail, have been synthesized and studied. Both series were compared with the corresponding series with two saturated terminal alkyl tails. All the compounds have a bent central 1,3‐phenylene bis(4‐benzoyloxy)benzoate core; their mesophases were characterized by polarizing optical microscopy, differential scanning calorimetry, X‐ray diffraction and switching current response experiments. In all four series one of the terminal tails is varied from OC₈H₁₇ to OC₁₆H₃₃. The other terminal tails are OC₁₁H₂₃, O(CH₂)₉CH?=?CH₂, OC₁₀H₂₁ and O(CH₂)₈CH?=?CH₂. The short‐tailed compounds show monotropic or enantiotropic B₁ phases and the long‐tailed compounds the B₂ phase. The introduction of one terminal vinyl group slightly lowers the transition temperatures. The introduction of a second terminal vinyl group further suppresses the liquid crystalline properties. All compounds with B₂ phases have layer spacings that suggest a tilt of ～45° of the bent molecules in the layers, and their switching behaviour is antiferroelectric.     

Twist-bend nematics,liquid crystal dimers,structure–property relations

ABSTRACT

One of the current challenges in liquid crystal science is to understand the molecular factors leading to the formation of the intriguing twist-bend nematic phase (N_TB) and determine its properties. During our earlier hunt for the N_TB phase created on cooling directly from the isotropic phase and not the nematic phase, we had prepared 30 symmetric liquid crystal dimers. These had odd spacers and methylene links to the two mesogenic groups; desirable but clearly not essential features for the formation of the N_TB. Here, we report the phases that the dimers exhibit and their transition temperatures as functions of both the lengths of the spacer and the terminal chains. In addition we describe the transitional entropies, their optical textures, the X-ray scattering patterns and the ²H NMR spectra employed in characterising the phases. All of which may lead to important properties of the twist-bend nematic phase.     

Magnetic field‐assisted liquid crystal alignment on a solid substrate: drift of easy orientation axis,anchoring energy and angular distribution of adsorbed liquid crystal molecules

The anchoring properties of a film of anisotropically adsorbed liquid crystal (LC) molecules on a rigid substrate have been studied. The LC film was prepared by cooling it from the isotropic phase in the presence of a magnetic field parallel to the surface of the substrate. Relationship between the anchoring energy, easy axis direction and angular distribution of the adsorbed molecules, and changes in their angular distribution due to adsorption–desorption, were studied. The dependence of the anchoring energy on the duration and the temperature at which the LC film is annealed allowed an estimation of the activation energy of desorption of LC molecules on ITO surface, ΔE≈0.55 eV. The results suggest that hydrogen bonds are responsible for the adsorption of LC molecules on the substrate.     

Oscillating Poiseuille flow in photo‐aligned liquid crystal cells

We present an experimental study of thin liquid crystal (LC) layers under the action of a harmonically varied pressure gradient. Optical measurements were performed to register the linear oscillations of a nematic director related to homeotropic and homeoplanar (hybrid) initial states. In the latter case one of the inner surfaces of the rectangular channels was treated by ultraviolet light to provide a relatively weak planar anchoring. The optical response of hybrid and homeotropic LC cells under an oscillating pressure gradient was investigated in relation to on the amplitude and frequency of the pressure gradient. A hydrodynamic model is developed taking into account the LC polar anchoring strength and the surface viscosity responsible for a fast LC surface dynamics. Our estimates show that the thickness of the boundary layer corresponding to the surface viscosity does not exceed 10^?6 m, and further experiments are needed with thinner LC cells and higher frequency oscillations to achieve a more precise value. An oscillating Poiseuille flow in the hybrid cell was found to be useful for characterizing elastic and viscous properties of a weakly anchoring LC surface layer in a fast surface dynamic process.     

Cell gap‐dependent transmission characteristics of a fringe‐electric field‐driven homogeneously aligned liquid crystal cell,for a liquid crystal with negative dielectric anisotropy

Transmittance characteristics were studied as a function of cell gap for a homogeneously aligned liquid crystal (LC) cell driven by a fringe‐electric field—named fringe‐field switching (FFS) mode. The light efficiency of a conventional LC cell using in‐plane switching and twisted nematic modes, where the LC director is determined by competition between elastic energy and electrical energy, does not depend on cell gap as long as the cell retardation value remains the same; i.e. only dielectric torque contributes to the deformation of the LC director. However, the transmittance of the FFS mode is dependent on the cell gap such that it decreases as the cell gap decreases, although the cell retardation value remains the same. This unusual behaviour (unlike that of conventional LC cells) arises because in the device the elastic and dielectric torques have the role of determining the LC director, such that the driving voltage giving rise to maximum transmittance becomes strongly dependent on the electrode position when the cell gap is as small as 2?µm. In addition, the LCs at the centre of the pixel and common electrodes are not sufficiently twisted because of a competition between the two elastic forces, which tries to twist the LCs in plane and hold them in their initial state by surface anchoring.     

Synthesis and liquid crystal properties of some 2,6‐disubstituted anthracenes

The synthesis and liquid crystalline properties of some new 2,6‐disubstituted anthracenes are described. Symmetrical alkylphenyl derivatives exhibit smectic mesophases, whereas simpler structures are non‐mesogenic. One unsymmetrically substituted anthracene exhibits a narrow nematic phase. The potential for these molecules to act as phototriggers has been investigated but efficient photodimerisation cannot be achieved.     

Rubbing angle effect on in‐plane switching liquid crystal displays

The rubbing angle effect on transmissive in‐plane switching liquid crystal displays is analysed by the Jones matrix method. Simulation results show that the optimum rubbing angle is around 30°–40°; the cell gap/birefringence product (dΔn) is about 0.33 µm. Increasing the rubbing angle can shorten the rise time and enlarge the grey scale voltage intervals. The optical characteristics are similar in two cells with different rubbing angles. These effects are particularly attractive for liquid crystal TV applications.     

Dynamics of the acousto‐optic effect in a nematic liquid crystal

In a nematic liquid crystal cell, the application of an ultrasonic wave induces a rotation of the director, leading to a change in the optical transmission through the cell. In this study, we investigate the dynamic response of the optical intensity after the ultrasonic wave is switched on or off. Our experiments show that the optical intensity follows a double‐exponential function of time, indicating that the system has two relaxation modes with widely different time scales. The fast mode has an amplitude and time scale qualitatively consistent with the dynamics of the Fréedericksz transition, but the slow mode shows novel behaviour associated with the acousto‐optic effect.     

High birefringence and high resistivity isothiocyanate‐based nematic liquid crystal mixtures

The molecular structures and physical properties of several single‐ and double‐fluorinated isothiocyanatotolane, isothiocyanatocyclohexyltolane, and isothiocyanatoterphenyl compounds are reported. Two eutectic mixtures comprising these compounds are formulated and their properties evaluated. These mixtures exhibit a high birefringence, relatively low viscosity, high resistivity, and good photo and thermal stabilities. Potential applications of these mixtures for spatial light modulators, optical phased arrays, and high speed photonics are discussed.     

Non‐linear electromechanical transformations and amplification acoustical signal in ferroelectric liquid crystals

Resonance systems with ferroelectric liquid crystal have been investigated, and the parametrisation of an oscillation system with resonance properties depending on ferroelectric liquid crystal properties has been investigated. The parametric amplifier of mechanical oscillations has been obtained for the first time. The results have been analysed using different existing theories of SmC* liquid crystal dynamics.     

Sub‐millisecond response phase modulator using a low crossover frequency dual‐frequency liquid crystal

A high birefringence (Δn = 0.292 at λ = 633 nm, 25°C) and low crossover frequency (<1 kHz at T = 25°C) dual‐frequency liquid crystal (DFLC) mixture was developed. The high birefringence enabled us to use a thin liquid crystal cell, which is helpful for fast response time and low operating voltage. The initially low crossover frequency allowed us to operate the DFLC device at an elevated temperature, which significantly lowers the viscosity while keeping the crossover frequency in an acceptable range (<10 kHz). We demonstrated a 2π phase shifter at λ = 633 nm using such a DFLC and obtained a sub‐millisecond response time at T～45°C. This type of DFLC mixture together with elevated temperature operation opens a new way for achieving fast response time.     

Calorimetric study of the isotropic to nematic phase transition in an aligned liquid crystal nano‐colloidal gel

A high‐resolution calorimetric study of the specific heat (C_p ) has been carried out for the isotropic to nematic phase transition in an aligned liquid crystal (octylcyanobiphenyl ‐ 8CB) and aerosil nano‐colloid gel. A stable alignment was achieved by repeated thermal cycling of the samples in the presence of a strong uniform magnetic field, which introduces anisotropy to the quenched random disorder of the silica gel. In general, the specific heat features of the I?N transition in aligned (anisotropic) gel samples are consistent with those seen in random (isotropic) gel samples, namely the observance of two C_p peaks and non‐monotonic transition temperature shifts with increasing silica concentration. However, larger transition temperature shifts with silica density, modification of the phase conversion process in the two‐phase coexistence region, and a larger effective transition enthalpy are observed for the aligned samples. The lower‐temperature aligned C_p peak is larger and broader while exhibiting less dispersion than the equivalent peak for the random gel. This may be a consequence of the alignment altering the evolution from random‐dilution‐dominated to random‐field‐dominated effects. The exact origin of the larger transition temperature shifts is uncertain but the larger enthalpy suggests that the nematic state is different in the aligned system than in random gels. The general non‐monotonic behaviour of the transition temperature is interpreted using dimensional analysis as a combination of an effective elastic stiffening of the liquid crystal combined with a liquid crystal and aerosil surface interaction energy.     

Synthesis and characterization of achiral banana‐shaped liquid crystalline molecules containing bisnaphthyl moieties

Three analogous series of symmetric banana‐shaped liquid crystalline molecules containing bisnaphthyl units were synthesized and characterized. The effects of linking groups (on the side wings) and lateral meta‐fluoro substitutions (on the middle outer rings) on the mesogenic properties were examined. The type of mesophase depends on the lengths of terminal alkoxy chains. Thus, achiral molecules with shorter flexible chains (n = 8) exhibit a rectangular columnar (B₁) phase, while analogous derivatives with longer flexible chains (n = 12) display the B₂ phase. All lateral meta‐fluoro substituted analogues (series II) possess the lowest isotropization temperatures and the narrowest mesophasic ranges of the B₁ and B₂ phases. The B₁ and B₂ phases were confirmed by X‐ray diffraction, polarizing optical microscopy (POM) and electro‐optical (EO) switching experiments. An electric field‐induced transition from an antiferroelectric (tristable) state to a ferroelectric (bistable) state was observed in the EO measurements. Spontaneous polarization (by switching current response), tilt angle of chiral domains (by POM), and transmittance–voltage measurements of the B₂ phase in related compounds have been surveyed in this study.     

Improving the electro‐optical properties of bistable reflective cholesteric liquid crystal displays

We have improved the electro‐optical properties of a bistable cholesteric liquid crystal display (Ch‐LCD) that is driven by a 3+2 dynamic driving scheme (3+2 DDS). The best contrast ratio is achieved at the selection period of 1.2–1.5 ms/line and the temperature range 26–30°C. The suitable preparation period and evolution period for contrast ratio are 40 times and 20 times the selection time, respectively. In the 3+2 DDS, rubbing the homeotropic alignment layer increases reflectivity of the ON state and keeps the reflectivity of the OFF state at the same level, so reflectivity and contrast ratio alike increase as a result. However, in a delayed homeotropic reset driving method, when the homeotropic alignment layer is rubbed, the reflectivity of both the ON and OFF states increases, thus the contrast ratio decreases. The combination of driving method and aligned surface morphology influences the relaxation mechanism in the cholesteric texture. By optimizing panel condition, we have demonstrated an 8.4″ foldable VGA Ch‐LCD that exhibits high reflectivity and contrast ratio with an addressing speed of around 1.2 ms/line.     

A graph‐theoretical approach to statistics and dynamics of tree‐like molecules

We present a new graphtheoretical method for calculating the dynamical and statistical properties of a Gaussian chain with various molecular architecture. The characteristic polynomial for its line graph, which has the bonds of a molecular graph as its beads with adjacency of bonds as in the graph, makes it possible to provide us with the general equation for calculating the radius of gyration of Gaussian chains and their relaxation spectra.