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.

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.

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.

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.

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.

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.

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.

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.

Definite existence of subphases with eight- and ten-layer unit cells as studied by complementary methods, electric-field-induced birefringence and microbeam resonant x-ray scattering.

A mixture of two selenium-containing compounds, 80 wt. % AS657 and 20 wt. % AS620, are studied with two complementary methods, electric-field-induced birefringence (EFIB) and microbeam resonant x-ray scattering (µRXS). The mixture shows the typical phase sequence of Sm-C_{A}^{*}-1/3-1/2-Sm-C^{*}-Sm-C_{α}^{*}-Sm-A, where 1/3 and 1/2 are two prototypal ferrielectric and antiferroelectric subphases with three- and four-layer unit cells, respectively. Here we designate the subphase as its q_{T} number defined by the ratio of [F]/([F]+[A]), where [F] and [A] are the numbers of synclinic ferroelectric and anticlinic antiferroelectric orderings in the unit cell, respectively. The electric field vs temperature phase diagram with EFIB contours indicates the emergence of three additional subphases, an antiferroelectric one between Sm-C_{A}^{*} and 1/3 and antiferroelectric and apparently ferrielectric ones between 1/3 and 1/2. The simplest probable q_{T}'s for these additional subphases are 1/4, 2/5, and 3/7, respectively, in the order of increasing temperature. The µRXS profiles indicate that antiferroelectric 1/4 and 2/5 approximately have the eight-layer (FAAAFAAA) and ten-layer (FAFAAFAFAA) Ising unit cells, respectively. The remaining subphase may be ferrielectric 3/7 with a seven-layer unit cell, although the evidence is partial. These experimental results are compared with the phenomenological Landau model [P. V. Dolganov and E. I. Kats, Liq. Cryst. Rev. 1, 127 (2014)2168-039610.1080/21680396.2013.869667] and the quasimolecular model [A. V. Emelyanenko and M. A. Osipov, Phys. Rev. E 68, 051703 (2003)1063-651X10.1103/PhysRevE.68.051703].

Transitional subphases near the electric-field-induced phase transition to the ferroelectric phase in Se-containing chiral smectic liquid crystals observed by resonant x-ray scattering.

Resonant x-ray scattering experiments revealed transitional subphases near the electric-field-induced phase transition of a Se-containing chiral liquid crystal in a planar aligned cell geometry. In the lower-temperature range (Sm-C_{A}^{*} and three-layer periodicity Sm-C_{γ}^{*} phases), the six-layer periodicity subphase appeared with increasing electric field during the field-induced transition from Sm-C_{γ}^{*} to Sm-C^{*}. In the higher-temperature range [four-layer periodicity antiferroelectric (AF) phase], the peak positions of the three-layer satellites shifted to those of the four-layer satellites and then the satellites corresponding to the five- through seven-layer periodicity appeared in sequence. Near the AF to Sm-C_{α}^{*} phase transition temperature, the layer periodicity increased with applied field. The molecular configurations of the subphases near the field-induced transition are discussed based on the Ising, distorted clock, and perfect clock models.

Optically Isotropic Homochiral Structure Produced by Intercalation of Achiral Liquid Crystal Trimers.

Dark conglomerates of domains with opposite handedness, which are designated dark conglomerate phases (DC phases), have attracted much attention. We prepared an achiral liquid crystal trimer, 4,4'-bis{9-[4-(5-octyloxypyrimidin-2-yl)phenyloxy]nonyloxy}biphenyl (I-9), and investigated the physical properties. A droplet of trimer I-9 formed a conventional nematic phase on cooling from the isotropic liquid, and then changed to an optical isotropic phase with homochirality. X-ray diffraction measurements reveal that the isotropic phase has an intercalated layer structure with a correlation length of 95 nm. We prepared binary mixtures with a nematic liquid crystal, 4'-hexyloxy-4-cyanobiphenyl (6OCB). The mixtures containing 30-75 mol % of 6OCB exhibited smectic phases above the isotropic phase. We investigated mesogenic properties of trimer I-n (n = 5-9) depending on the parity of the linking group. Only trimer I-9 possessing the longest odd-numbered spacers showed the chiral isotropic phase, suggesting that a rigid bent structure is not necessary for the appearance of the isotropic phase. The experimental results reveal that trimer I-9 exhibits a soft crystalline DC phase representing a new modification of chiral symmetry breaking in lamellar liquid crystal phases.

Effective long-range interlayer interactions and electric-field-induced subphases in ferrielectric liquid crystals.

Microbeam resonant x-ray scattering experiments recently revealed the sequential emergence of electric-field-induced subphases (stable states) with exceptionally large unit cells consisting of 12 and 15 smectic layers. We explain the emergence of the field-induced subphases by the quasimolecular model based on the Emelyanenko-Osipov long-range interlayer interactions (LRILIs) together with our primitive way of understanding the frustration in clinicity using the q_{E} number defined as q_{E}=|[R]-[L]|/([R]+[L]); here [R] and [L] refer to the numbers of smectic layers with directors tilted to the right and to the left, respectively, in the unit cell of a field-induced subphase. We show that the model actually stabilizes the field-induced subphases with characteristic composite unit cells consisting of several blocks, each of which is originally a ferrielectric three-layer unit cell stabilized by the LRILIs, but some of which would be modified to become ferroelectric by an applied electric field. In a similar line of thought, we also try to understand the puzzling electric-field-induced birefringence data in terms of the LRILIs.

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.

Supermolecular bent configuration composed of achiral flexible liquid crystal trimers exhibiting chiral domains with opposite handedness.

Chirality's effects on physical properties of materials and how chirality arises have persisted as attractive issues in chemistry. We prepared a homologous series of achiral liquid crystal trimers in which three phenylpyrimidine units are connected via flexible heptamethylene spacers. An equimolecular mixture of a trimer with a nematic (N) phase and that with smectic A (SmA), smectic C (SmC), and smectic B phases was found to exhibit an N phase, a SmC phase, and a B4 phase composed of chiral domains with opposite handedness. The chiral characteristics of the B4 phase were confirmed by uncrossing the polarizers in opposite directions. XRD measurements reveal that both SmC and B4 phases have an interdigitated layer structure. That molecular interdigitation might form a supermolecular bent configuration that can produce saddle splay curvature to drive the B4 phase.

Layer modulated smectic-C phase in liquid crystals with a terminal hydroxyl group.

We investigated local layer structures of the three smectic-C phases (SmC, SmC', and SmC″) in a liquid crystal with the terminal hydroxyl group using high resolution and microbeam x-ray diffraction. It is found that SmC is the conventional SmC1 phase and SmC″ is the bilayer SmC2 phase. The SmC' phase forms an in-plane modulation structure, so that this phase is the smectic-C antiphase. From the Fourier transform infrared spectroscopy, it is suggested that the intermolecular hydrogen bonding is important to induce the SmC' and SmC″ phases.