Hideo Takezoe

A Twist-Bend Nematic (NTB) Phase of Chiral Materials†

New chiral dimers consisting of a rod-like and cholesterol mesogenic units are reported to form a chiral twist-bend nematic phase (NTB *) with heliconical structure. The compressibility of the NTB phase made of bent dimers was found to be as large as in smectic phases, which is consistent with the nanoperiodic structure of the NTB phase. The atomic force microscopy observations in chiral bent dimers revealed a periodicity of about 50 nm, which is significantly larger than the one reported previously for non-chiral compounds (ca. 10 nm).

Optically driven translational and rotational motions of microrod particles in a nematic liquid crystal

Significance This paper addresses light-driven dynamic motions of microrods suspended in a liquid crystal (LC) host. The results presented in this paper advance molecular-assisted manipulations of colloidal particles and their assemblies, which is a key concept for smart microdevices, using their interplay with the topology of the nematic director field. Almost all previous studies on colloids in LC (except some work by Yamamoto et al.) have dealt with the observation and analysis of defect structures around colloid particle(s) with fixed anchoring conditions. Herein we use a photoactive surfactant, which enables control of the LC anchoring by light irradiation. The induced reversible anchoring transition is accompanied by a reorientation of the rods and/or their translational motion. A small amount of azo-dendrimer molecules dissolved in a liquid crystal enables translational and rotational motions of microrods in a liquid crystal matrix under unpolarized UV light irradiation. This motion is initiated by a light-induced trans-to-cis conformational change of the dendrimer adsorbed at the rod surface and the associated director reorientation. The bending direction of the cis conformers is not random but is selectively chosen due to the curved local director field in the vicinity of the dendrimer-coated surface. Different types of director distortions occur around the rods, depending on their orientations with respect to the nematic director field. This leads to different types of motions driven by the torques exerted on the particles by the director reorientations.

Short-range smectic fluctuations and the flexoelectric model of modulated nematic liquid crystals

We show that the flexoelectric model of chiral and achiral modulated nematics predicts the compression modulus that is by orders of magnitude lower than the measured values. The discrepancy is much larger in the chiral modulated nematic phase, in which the measured value of the compression modulus is of the same order of magnitude as in achiral modulated nematics, even though the heliconical pitch is by an order of magnitude larger. The relaxation of a one-constant approximation in the biaxial elastic model used for chiral modulated nematics does not solve the problem. Therefore, we propose a structural model of the modulated nematic phase, which is consistent with the current experimental evidence and can also explain large compression modulus: the structure consists of short-range smectic clusters with a fourfold symmetry and periodicity of two molecular distances. In chiral systems, chiral interactions lead to a helicoidal structure of such clusters.

Chiral Superstructure Mesophases of Achiral Bent-Shaped Molecules – Hierarchical Chirality Amplification and Physical Properties

Chiral mesophases in achiral bent-shaped molecules have attracted particular attention since their discovery in the middle 1990s, not only because of their homochirality and polarity, but also due to their unique physical/physicochemical properties. Here, the most intriguing results in the studies of such symmetry-broken states, mainly helical-nanofilament (HNF) and dark-conglomerate (DC) phases, are reviewed. Firstly, basic information on the typical appearance and optical activity in these phases is introduced. In the following section, the formation of mesoscopic chiral superstructures in the HNF and DC phases is discussed in terms of hierarchical chirality. Nanoscale phase segregation in mixture systems and gelation ability in the HNF phase are also described. In addition, some other related chiral phases of bent-shaped molecules are shown. Recent attempts to control such mesoscopic chiral structure and the alignment/confinement of HNFs are also discussed, along with several examples of their fascinating advanced physical properties, i.e. huge enhancement of circular dichroism, electro- and photo-tunable optical activities, chirality-induced nonlinear optics (second-harmonic-generation circular difference and electrogyration effect), enhanced hydrophobicity through the dual-scale surface morphological modulation, and photoconductivity in the HNF/fullerene binary system. Future prospects from basic science and application viewpoints are also indicated in the concluding section.

Optical manipulation of the nematic director field around microspheres covered with an azo-dendrimer monolayer.

We report here the optical manipulation of the director and topological defect structures of nematic liquid crystals around a silica microparticle with azobenzene-containing dendrimers (azo-dendrimers) on its surface. We successfully demonstrate the successive switching processes from hedgehog, to boojum, and further to Saturn ring configurations by ultraviolet (UV) light irradiation and termination. The switching time between these defect structures depends on the UV light intensity and attains about 50 ms. Since the pretreatment of microparticles is not necessary and the surface modification is spontaneously performed just by dissolving the azo-dendrimers in liquid crystals, this dendrimer supplies us with a variety of possible applications.

Historical Overview of Polar Liquid Crystals

Brief history of ferroelectric and antiferroelectric liquid crystals is described. To reduce the symmetry of the molecular systems, two ideas were successfully used; introductions of chirality and molecular shape asymmetry. The chirality introduced into rod-shaped and disc-shaped molecular systems led to chiral smectic C and chiral discotic columnar phases. Dogleg from rod and cone or bowl from disc in molecular shapes brought about polar organization by their packing, realizing so-called banana phases and polar columnar phases, respectively. Particularly, bent-core mesogens exhibit a variety of novel polar phases. In addition to such established polar structures, some evidences about polar structures realized in polar nematic and cholesteric phases are given in some detail. Attempts for the application of these polar liquid crystals such as displays are also overviewed.

Monolayer Filaments versus Multilayer Stacking of Bent‐Core Molecules

Bent-core materials exhibiting lamellar crystals (B4 phase), when dissolved in organic solvents, formed gels with helical ribbons made of molecular monolayers and bilayers, whereas strongly deformed stacks of 5-6 layers were found in the bulk samples. The width and pitch of the helical filaments were governed by molecular length; they both increased with terminal-chain elongation. It was also found that bulk samples were optically active, in contrast to the corresponding gels, which lacked optical activity. The optical activity of samples originated from the internal structure of the crystal layers rather than from the helicity of the filaments. A theoretical model predicts a strong increase in optical activity as the number of layers in the stack increases and its saturation for few layers, thus explaining the smaller optical activity for gels than for bulk samples. A strong increase and redshift in fluorescence was detected in gels as compared to the sol state.

Electrophoretic Deposition for Cholesteric Liquid-Crystalline Devices with Memory and Modulation of Reflection Colors.

The first design strategy that allows both memorization and modulation of the liquid-crystalline reflection color is reported. Electrophoretic deposition of a tailored ionic chiral dopant is key to realizing this unprecedented function, which may pave the way for the development of full-color e-paper that can operate without the need of color filters.

Lasing properties of polymerized chiral nematic Bragg onion microlasers

Dye doped photocurable cholesteric liquid crystal was used to produce solid Bragg onion omnidirectional lasers. The lasers were produced by dispersing and polymerizing chiral nematic LC with parallel surface anchoring of LC molecules at the interface, extracted and transferred into another medium. Lasing characteristics were studied in carrier medium with different refractive index. The lasing in spherical cholesteric liquid crystal was attributed to two mechanisms, photonic bandedge lasing and lasing of whispering-gallery modes. The latter can be suppressed by using a higher index carrier fluid to prevent total internal reflection on the interface of the spheres. Pulse-to-pulse stability and threshold characteristics were also studied and compared to non-polymerized lasers. The polymerization process greatly increases the lasing stability.

Enhancement of the helical twisting power with increasing the terminal chain length of nonchiral bent-core molecules doped in a chiral nematic liquid crystal

In this work, we prepared a series of nonchiral bent-core molecules with different terminal alkoxy chain lengths, and measured the helical twisting power (HTP) of the bent-core molecules doped in a chiral nematic liquid crystal (N*LC). We investigated the doping effect through the colour change and spectral change due to the Bragg (selective) reflection and found that the bent-core molecules with longer alkoxy chains showed stronger HTP under chiral circumstances such as N*LC. Namely, not only the axial conformations at wings linked to the bent central unit but also the length of the alkoxy chains at the terminal positions of the bent-core molecules play an important role in the resulting unusual chiral behaviour. A preliminary stochastic dynamics simulation to determine the distribution of the chirality order parameters was made, being consistent with the present experimental result.