Chiroptical Performances in Self-Assembled Hierarchical Nanosegregated Chiral Intermediate Phases Composed of Two Different Achiral Bent-Core Molecules.

In this paper, chiral intermediate phases composed of two achiral molecules are fabricated by utilizing nanophase separation and molecular hierarchical self-organization. An achiral bent-core guest molecule, exhibiting a calamitic nematic and a dark conglomerate phase according to the temperature, is mixed with another achiral bent-core host molecule possessing a helical nanofilament to separate the phases between them. Two nanosegregated phases are identified, and considerable chiroptical changes, such as circular dichroism and circularly polarized luminescence, are detected at the transition temperatures between the different nanophase-separated states. The nanosegregated chiral phase-wherein the helical nanofilament and dark conglomerate phases are phase-separated-exhibits the highest chiroptical intensities. The luminescence dissymmetry factor, |glum|, in this phase is amplified by an order of magnitude compared with that of another nanosegregated phase, wherein the helical nanofilament and nematic phases are phase-separated.

New liquid crystal formation induced by nanoscale phase separation composed of bent-core liquid crystal and rod-like cholesteric liquid crystal mixtures.

Herein, the local nano-structure in mixtures of a cholesteric liquid crystal mixture and a bent-core molecule was analyzed via the small-angle X-ray scattering. Accordingly, different types of orientational X-ray patterns were obtained, suggesting the different types of nanoscale phase separation, which depends on the cooling rate from the isotropic phase, and thus is related with the kinetics of the phase separation process. Particularly, in the gradual cooling process, a new structure with smectic order in the phase-separated system stably appeared, which is considered to be caused by the B4 filament. According to the structure analysis, it was found that the system composed of rod-like and bent-core molecules not only undergoes simple phase separation, but also an unexpected new functional structure can be constructed by the strong interaction.

Structural transformations in tetravalent nematic shells induced by a magnetic field.

The role of applied fields on the structure of liquid crystals confined to shell geometries has been studied in past theoretical work, providing strategies to produce liquid crystal shells with controlled defect structure or valence. However, the predictions of such studies have not been experimentally explored yet. In this work, we study the structural transformations undergone by tetravalent nematic liquid crystal shells under a strong uniform magnetic field, using both experiments and simulations. We consider two different cases in terms of shell geometry and initial defect symmetry: (i) homogeneous shells with four s = +1/2 defects in a tetrahedral arrangement, and (ii) inhomogeneous shells with four s = +1/2 defects localized in their thinner parts. Consistently with previous theoretical results, we observe that the initial defect structure evolves into a bipolar one, in a process where the defects migrate towards the poles. Interestingly, we find that the defect trajectories and dynamics are controlled by curvature walls that connect the defects by pairs. Based on the angle between Bs, the local projection of the magnetic field on the shell surface, and n+½, a vector describing the defect orientations, we are able to predict the nature and shape of those inversion walls, and therefore, the trajectory and dynamics of the defects. This rule, based on symmetry arguments, is consistent with both experiments and simulations and applies for shells that are either homogeneous or inhomogeneous in thickness. By modifying the angle between Bs and n+½, we are able to induce, in controlled way, complex routes towards the final bipolar state. In the case of inhomogeneous shells, the specific symmetry of the shell allowed us to observe a hybrid splay-bend Helfrich wall for the first time.

Linear symmetric liquid crystal trimers exhibiting supramolecular chiral architectures.

We prepared a homologous series of achiral liquid crystal trimers (I-n) in which two phenylpyrimidine units and one biphenyl unit were connected via flexible spacers, and investigated the physical properties. All the trimers possessing odd-numbered methylene spacers exhibited soft crystalline chiral conglomerate phases. X-ray diffraction measurements reveal that they have an intercalated layer structure. On the other hand, the trimers possessing even-numbered spacers showed nematic and smectic C phases. We investigated the surface structures of odd-membered trimers in the soft crystalline phases using scanning electron microscopy. Trimers I-3 and I-5 were found to form cylindrical tubes, whereas trimers I-7, I-9 and I-11 toroidal pits. We discuss the formation of diverse supramolecular architectures in terms of the anisotropy of the chirality transfer.

Unique Superparamagnetic-like Behavior Observed in Non-π-delocalized Nitroxide Diradical Compounds Showing Discotic Liquid Crystalline Phase.

A unique superparamagnetic-like behavior and a large "positive magneto-LC effect" were observed in the solid phases and the hexagonal columnar (Colh ) liquid crystalline (LC) phase, respectively, of novel achiral non-π-delocalized nitroxide diradical compounds (R,S)-1, which showed polymorphism in the solid phases (solids I and II). The SQUID magnetization measurement revealed that (1) (R,S)-1 containing a small amount of racemic diastereomers (R*,R*)-1 possessed an unusual and large temperature-independent magnetic susceptibility (χTIM >0) component in the original nanocrystalline solid I that was responsible for the observed superparamagnetic-like behavior under low magnetic fields and did not arise from the contamination by extrinsic magnetic metal or metal ion impurities, besides ordinary temperature-dependent paramagnetic susceptibility (χpara >0) and temperature-independent diamagnetic susceptibility (χdia <0) components, (2) a large increase in molar magnetic susceptibility (χM ) (positive magneto-LC effect) that occurred at the solid I-to-liquid crystal transition upon heating was preserved as an additional χTIM increase in the resulting polymorphic nanocrystalline solid II by cooling, and (3) such unique magnetic phenomena were induced by thermal processing for (R,S)-1 or by adding a small amount of (R*,R*)-1 to (R,S)-1 as the impurity.

Achiral flexible liquid crystal trimers exhibiting gyroid-like surfaces in chiral conglomerate phases.

Chiral conglomerate phases have attracted much attention not only for the spontaneous mirror symmetry breaking but also for their nanostructures. We investigated both surface and bulk structures of a homologues series of an achiral liquid crystal trimer I-(n,m) exhibiting soft crystalline chiral conglomerate phases by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The trimers were found to form bicontinuous networks. In particular, trimer I-(9,9) exhibited a single gyroid-like surface accompanying periodic distribution of dimples with a size of about 100 nm. It showed a sponge-like structure in the bulk of the material. The twist conformation of the flexible trimer I-(n,m) can cause layer deformation, which produces bicontinuous networks exhibiting optical activity.

A frustrated phase driven by competition among layer structures.

Using our designed ternary system consisting of a semiperfluorinated smectic liquid crystal and two nematic liquid crystals, we investigated their phase transition behaviour using polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction. A mixture containing 20 mol% of the semiperfluorinated compound was found to exhibit the following unusual phase sequence: isotropic liquid - isotropic liquid + smectic A phase - nematic phase - unidentified frustrated phase (X) - modulated phase (Y) - modulated phase (Z). The frustrated phase showed a fan-shaped texture characteristic of a smectic phase, but no peak corresponding to the layer spacing was detected. No difference was found in the shearing stress between the high-temperature N phase and the frustrated phase, but electro-optical switching observed in the N phase was not detected in the frustrated phase. We discuss how the molecules organize the unusual phase transition behaviour.

Achiral flexible liquid crystal trimers exhibiting chiral conglomerates.

Chiral conglomerates of domains with opposite handedness have attracted much attention from researchers. We prepared a homologous series of achiral liquid crystal trimers in which two phenylpyrimidine units and one biphenyl unit were connected via flexible methylene spacers. We investigated their phase transition behaviour. Some trimers possessing odd-numbered spacers were found to exhibit a nematic phase and a dark chiral conglomerate phase possessing a layered structure. The chiral characteristics were confirmed by uncrossing the polarizers in opposite directions. The layer spacing detected using X-ray diffraction was about 80% of the molecular length. The structure-property relations indicate that intermolecular interactions cause a conformational change in the trimers possessing flexible odd-numbered methylene spacers to form helical conformers with axial chirality, which might induce chiral segregation and layer deformation to drive the chiral conglomerates.

Chiral conglomerates observed for a binary mixture of a nematic liquid crystal trimer and 6OCB.

Dark conglomerates of domains with opposite handedness, which are designated as dark conglomerate phases (DC phases), have attracted much attention. After designing an achiral liquid crystal trimer, 4,4'-bis{7-[4-(5-octyloxypyrimidin-2-yl)phenyloxy]heptyloxy}biphenyl (1), which exhibits only a nematic phase, we prepared binary mixtures with some typical rod-like nematic liquid crystals, i.e., 4'-hexyloxy-4-cyanobiphenyl (6OCB), 2-(4-hexyloxyphenyl)-5-pentyloxypyrimidine (PPY), or 4-methyloxyphenyl 4-hexyloxycyclohexanecarboxylate (PCA), and investigated their phase transition behaviour. The binary mixtures containing 55­90 mol% of 6OCB were found to exhibit a nematic phase and a DC phase of chiral domains with opposite handedness. However, neither PPY nor PCA induced such a chiral conglomerate phase in the mixture with trimer 1. We discuss how core­core interactions contribute to produce such a chiral conglomerate phase.

The effect of the structure of a helical nanofilament of the B4 phase of bent-core liquid crystals on the nano-phase separation mixed with a rod-like cholesteric liquid crystal mixture.

We studied the structure of a helical nano-filament of the B4 phase in mixtures of a cholesteric liquid crystal mixture and a bent-core molecule using a resonant soft X-ray scattering (RSoXS) technique. In this system, nanophase separation occurs and it was already found that an unexpected new functional chiral smectic structure in the rod-like molecule rich region is constructed by the strong interaction between bent-core and rod-like molecules. In this paper, we focused on the structure of the helical filament in the bent-core liquid crystalline molecule rich region in this mixing system, and it was found that the pitch of the helical filament decreases and the coherence of the helical structure increases.

Molecular manipulator driven by spatial variation of liquid-crystalline order.

Collective long-range interactions between micrometre-sized impurities in liquid crystals result from the elastic distortion of the liquid-crystalline order. For substantially smaller polymeric impurities, what is relevant is not the elastic interaction between them but the coupling between the scalar nematic order parameter S and the polymer concentration φ. This coupling originates from local molecular interactions, but becomes long ranged because the total polymer concentration is conserved over the whole sample. Here, we propose a new mechanism by which the spatial variation of S generates a force, mediated by the coupling between S and φ, that transports nanoscale polymeric impurities. We have designed a prototype of a molecular manipulator that moves molecules along spatial variations of the scalar order parameter, modulated in a controlled manner by spot illumination of an azobenzene-doped nematic phase with ultra-violet light. We also demonstrate the use of the manipulator for the measurement of the anisotropic diffusion constant of a polymer in the nematic phase. The manipulator can control the spatial variation of the polymer concentration, thus showing promise for use in the design of hybrid soft materials.

Variety of subphase emerging sequences, the frustration of three main phases, SmC_{A}

Prompted by the existence of biaxial subphases 1/4, 2/5, and 3/7 [Phys. Rev. E 96, 012701 (2017)2470-004510.1103/PhysRevE.96.012701], we reconsidered the three-phase frustration and the resulting degeneracy lifting by combining the phase diagram of SmC_{A}^{*}, SmC^{*}, and SmA with the discrete flexoelectric effect. We systematically calculated the phase diagrams and tried to understand the overall picture of the phenomena by means of a simple and intuitively clear way in terms of minimal number of parameters. The treatment naturally explains the highly distorted helical structures of the biaxial subphases as well as the microscopic helical short-pitch of SmC_{α}^{*} which increases or decreases accordingly with rising temperature. The regular subphase emerging sequence is SmC_{A}^{*}(SmC_{α}^{*})-1/4-1/3-2/5-3/7-1/2-SmC^{*}(SmC_{α}^{*}), where the subphases other than 1/3 and 1/2 may or may not emerge. At the same time, we can see a variety of irregular sequences; in particular, any one of the biaxial subphases may singly emerge between SmC_{A}^{*}(SmC_{α}^{*}) and (SmC^{*})SmC_{α}^{*}. Moreover, the experimentally confirmed extraordinary subphase emerging sequence SmC^{*}-1/2-SmC_{α}^{*} appears for particular parameter values. Contrastingly to these affirmative aspects, some calculated results are contradictory to the previously reported experimental results: the change from SmC_{A}^{*} and SmC^{*} to SmC_{α}^{*} is always continuous, the 6-layer 2/3 subphase is not stabilized, and the subphase emerging sequence SmC_{A}^{*}-1/3-SmC^{*} does not appear. The causes of inconsistency and how to resolve them were discussed in comparisons with experimental findings.

Conformation-Changeable π-Electronic Systems with Metastable Bent-Core Conformations and Liquid-Crystalline-State Electric-Field-Responsive Properties.

This study focused on the use of nonconventional bent-core π-electronic systems, 2,2'-bipyrroles substituted with modified benzoyl units, as building units of stimuli-responsive assemblies. Electric-field-responsive mesophase behaviors were observed in homochiral synclinic ferroelectric smectic C structures comprising the syn conformations. Electric-field application induced changes in the polarized optical microscopy textures with dynamic behaviors derived from the conversion from twisted to untwisted states.

Low threshold lasing from dye-doped cholesteric liquid crystal multi-layered structures.

We fabricated novel hybrid structures composed of a dye-doped low-molecular-weight cholesteric liquid crystal sandwiched by multi-layered polymer cholesteric liquid crystal films and evaluated their lasing characteristics. Lasing was observed with an extremely reduced threshold (12 nJ/pulse) by a factor of 10 compared with that in a simple dye-doped low-molecular-weight cholesteric liquid crystal cell. Lasing characteristics experimentally obtained were discussed by comparing them with the simulated photonic density of states spectra.

Unexpected electric-field-induced antiferroelectric liquid crystal phase in the SmC_{α}

The unique nanometer-sized helical structure in SmC_{α}^{*} may sometimes evolve continuously to the micrometer-sized one in SmC^{*}; conceivably ferroelectric SmC_{α}^{*} is to be unwound by an applied electric field. By drawing electric-field-induced birefringence contours in the field-temperature phase diagram and by studying the superlattice structure of the field-induced subphase with resonant x-ray scattering, we established that an applied field unexpectedly stabilizes the well-known antiferroelectric four-layer biaxial subphase as well as the other prototypal ferrielectric three-layer one in the SmC_{α}^{*} temperature range; the effective long-range interlayer interaction due to the discrete flexoelectric effect actually plays an important role in stabilizing not only the biaxial subphases but also the optically uniaxial SmC_{α}^{*} subphase, contrary to the notion that the competition between the direct interactions of the nearest-neighbor layers and those of the next-nearest-neighbor layers should be required for the nanometer-sized helical structure.

Alternating twist structures formed by electroconvection in the nematic phase of an achiral bent-core molecule.

We report an unusual electroconvection in the nematic phase of a bent-core liquid crystal. In a voltage-frequency diagram, two frequency regions exhibiting prewavy stripe patterns were found, as reported by Wiant We found that these stripes never show extinction dark when cells were rotated under crossed polarizers. Based on the color interchange in between neighboring stripes by the rotation of the cells or an analyzer, twisted molecular orientation is suggested; i.e., the directors are alternately twisted from the top to the bottom surfaces with a pretilt angle in adjacent stripes, which is an analogue of the twisted (splayed) structure observed in surface-stabilized ferroelectric liquid crystal cells. The transmittance spectra calculated using the 4x4 matrix method from the model structure are consistent with the experimental observation.

Resonant x-ray scattering observation of transitional subphases during the electric-field-induced phase transition in a mixture of Se-containing chiral smectic liquid crystals.

Using resonant x-ray scattering techniques, transitional subphases during the electric-field-induced phase transition of a mixture of Se-containing chiral liquid crystals, 80% AS657 and 20% AS620, in a planar-aligned cell geometry were investigated, where the prototypical phase sequence SmC_{A}^{*}-SmC_{γ}^{*}-AF-SmC^{*} was observed; the transitional subphases were formed during the transition from the three-layer periodicity phase to the ferroelectric phase. In the lower-temperature range where the three-layer SmCγ^{*} phase appeared under the low electric field, nine- and six-layer subphases and a "streak" pattern appeared in sequence after the transition from the SmCγ^{*} phase with increasing applied electric field; the ferroelectric phase was realized. In the higher-temperature range where the four-layer AF phase appeared under a low electric field, the AF phase changed to a three-layer phase at the medium electric field. The twelve-, nine-, and six-layer subphases subsequently appeared in sequence, and finally the ferroelectric phase was generated with increasing electric field. The molecular arrangements of the field-induced subphases, especially the newly found nine-layer periodicity phase, was analyzed. The successive field-induced phase transition of the present results was compared with that of our previous results for pure Se-containing and Br-containing liquid crystals, and the relation to the three-layer ferrielectric phase was discussed.

Simultaneous RGB reflections from single-pitched cholesteric liquid crystal films with Fibonaccian defects.

We introduce quasi-periodic Fibonaccian phase defects into single-pitched cholesteric liquid crystalline systems. Numerical simulations of reflection spectra from the proposed systems demonstrate simultaneous red, green, and blue reflections or multiple photonic band gaps. Fundamental optical properties are discussed as functions of phase jump (orientational defect angles), unit lengths and the orders of Fibonacci systems.

Structure of a B6-like phase formed from bent-core liquid crystals determined by microbeam x-ray diffraction.

We studied the structure of the Bx phase formed from the short terminal homolog, 1,3-(4-bromobenzene) bis[4-(4-n-butoxyphenylliminomethyl)benzoate] (4Br-P-4-O-PIMB), by focusing a microbeam of x ray on the well-developed fan-shaped texture. From the highly oriented x-ray patterns detected at the two states of DC-ON and DC-OFF, the Bx structure was definitely illustrated. It is a kind of frustrated one similar to the B1 phase: the molecules lie perpendicularly to the layer, and the frustration takes place perpendicularly to the bent direction. Unlike in the B1 phase, however, the size of the resulting antidomain is not definite, but fluctuates from position to position as observed in the B6 phase.

Three relaxation processes from an electric-field-induced polar structure in a columnar liquid crystalline urea derivative.

We have studied the polarization relaxation process after removing an applied electric field in the columnar hexagonal phase of N,N'-bis(3,4,5-trihexadecyloxyphenyl)urea by means of second-harmonic generation (SHG), switching current, and texture observation. Transient SHG and current associated by sudden field change show polarization switching associated with a molecular reorientation of about a few ms depending on the field strength. Furthermore, the texture observation reveals a column undulation process during 10 s to 1 min. The size of the polar domains was estimated to be 160 molecules by analyzing the field dependence of the SHG signal intensity on the basis of an Ising model.