Cybotactic Nematic Phase Research Articles

Search for microscopic and macroscopic biaxiality in the cybotactic nematic phase of new oxadiazole bent-core mesogens

The possibility of biaxial orientational order in nematic liquid crystals is a subject of intense current interest. We explore the tendencies toward local and global biaxial ordering in the recently synthesized trimethylated oxadiazole-based bent-core mesogens with a pronounced asymmetric (bow-type) shape of molecules. The combination of x-ray diffraction and optical studies suggests that the biaxial order is expressed differently at the short- and long-range scales. Locally, at the scale of a few molecules, x-ray-diffraction data demonstrate biaxial packing. However, above the mesoscopic scale, the global orientational order in all three compounds is uniaxial, as evidenced by uniform homeotropic alignment of the nematic phase which is optically tested over the entire temperature range and by the observations of topological defects induced by individual and aggregated colloidal spheres in the nematic bulk.

Rheological evidence for the existence of subphases in the liquid crystalline 4-n-alkoxybenzoic acids

ABSTRACTThe rheological behaviour of the homologous series, the alkyloxybenzoic acids, has been studied at steady flow and small amplitude oscillatory shear. The temperature dependencies of the viscosity were compared with differential scanning calorimetry data in order to estimate pretransitional phenomena in mesophases. The values of the viscosity and flow activation energy (E) can be indicative of the mesophase state. 4-n-pentyloxybenzoic acid yields a classic nematic (N) phase while the next homologues show a cybotactic nematic phase having a higher E value. The N phase is a Newtonian fluid of lower viscosity than that of the isotropic phase. The cybotactic nematic phase by its rheological properties takes an intermediate position between the N phase and a smectic C (SmC) phase. The SmC phase is a viscoelastic and viscoplastic medium. The SmC phase of 4-n-octyloxy-, 4-n-nonyloxy-, 4-n-decyloxy- and 4-n-dodecyloxybenzoic acid can exist in high- and low-ordered states. The more ordered smectic phase is characterised by higher stiffness, viscosity and yield stress than those of the less ordered. The SmC phase of 4-n-hexadecyloxybenzoic acid is characterised by the only state with unstable value of apparent viscosity. The phase state and the transition temperature can be dependent on the thermal history of the sample and a mechanical shear.

The effects of lateral halogen substituents on the low-temperature cybotactic nematic phase in oxadiazole based bent-core liquid crystals

We have previously demonstrated that the incorporation of lateral methyl groups on oxadiazole-based liquid crystals leads to relatively low-temperature cybotactic nematic phases which, in some cases, supercool to room temperature. We report here the synthesis and phase behaviour of related compounds that possess lateral halogen groups and in some cases, lateral methyl groups as well. Derivatives with three lateral substituents (one halogen and two methyl groups) in a specific pattern supercool in the nematic phase to room temperature. As was the case with the previously reported trimethylated derivatives, the low-temperature nematic phase is glassy in nature. Two of the new trisubstituted derivatives (with bromo and chloro groups) remain in the nematic phase upon subsequent heating until transitioning to the isotropic phase indicating that the low-temperature nematic phase may be more stable than that shown by the trimethylated analogue. Preliminary X-ray diffraction analysis confirms the presence of a tilted cybotactic nematic phase. In addition, the splitting observed in the wide-angle scattering feature is indicative of enhanced local biaxial packing.

Optical nonlinearity in the nematic phase of bent-core mesogens.

Nonlinear optical response of the cybotactic nematic phase of a bent-core mesogen has been investigated for the first time through self-phase modulation induced by a Gaussian beam. The material exhibits a high nonlinear response achieving a nonlinear index n(2)≈5×10(-5) cm(2)/W and an unconventional behavior characterized by two different regimes. While the high-intensity regime can be easily explained in terms of a thermal indexing effect, the low-intensity regime is metastable and characterized by an unusual dependence on the irradiation energy. It is suggested that a change of the director configuration, possibly due to a light-induced modification of surface anchoring, is responsible for the observed behavior.

ChemInform Abstract: The Cybotactic Nematic Phase of Bent‐Core Mesogens: State of the Art and Future Developments

AbstractReview: 44 refs.

Insights into Biaxial Ordering of Bent-Core Nematics: X-Ray Diffraction Evidence

Recently we have reported the first X-ray diffraction evidence of biaxial order in the fluid cybotactic nematic phase of a pair of trimethylated bent-core mesogens. This evidence is based on the splitting of the wide-angle diffuse scattering in the plane normal to the nematic director. The additional experimental data presented here provide further insights into this unprecedented behavior observed over the entire nematic phase. Although we could not determine the spatial extent of biaxial order—intracluster or intercluster—our observations reveal an enhanced biaxial orientational correlation in the transverse molecular packing, possibly reflecting stronger anisotropic interactions between nearest-neighbor mesogens.

Evidence of Biaxial Order in the Cybotactic Nematic Phase of Bent-Core Mesogens

In 2004 two reports of biaxiality in the nematic (N) phase of an oxadiazole-based bent-core mesogen (BCM) drew the attention of the scientific community to the unique freatures of bent-core nematics. Although a number of contradictory results have subsequently appeared in the literature, a general consensus has finally emerged on the conclusion that the unconventional properties of BCM nematics result from nanometer-size clusters of molecules (cybotactic groups), characterized by short-range smectic positional order and biaxial orientational order. Also, it has become evident that issues such as the development of transverse polar order, the appearance of biaxially ordered domains in a macroscopically uniaxial medium, the dramatic response to external electric and magnetic fields, are intimately related to the understanding and the search for biaxial thermotropic nematics. Hence, increasing the orientational correlation among cybotactic groups seems a viable strategy to obtain true (spontaneous and macroscopic) biaxial order.

1,2,4‐Oxadiazole‐Based Bent‐Core Liquid Crystals with Cybotactic Nematic Phases

Several series of bent-core mesogens derived from 3,5-diphenyl-1,2,4-oxadiazole with or without lateral groups and with different length terminal chains at both ends, and polycatenar molecules with three to six alkoxy chains are synthesized and their mesomorphic behaviour is investigated by polarizing microscopy, differential scanning calorimetry, X-ray diffraction (XRD), dielectric, electro-optical and second-harmonic generation (SHG) experiments. Most compounds exhibit broad regions of skewed cybotactic nematic (NcybC ) and tilted smectic (SmC) phases with a strong tilt of the aromatic cores (up to 63°), but non-tilted SmA and NcybA phases are also observed for a compound that has only one terminal chain. The XRD patterns of the nematic phases of most of the compounds investigated indicate a 2D periodicity with short correlation length in the magnetically aligned samples. This is of importance for the general interpretation of the small-angle XRD splitting patterns typically observed for aligned samples of bent-core nematic phases. In most nematic phases one current peak is observed in the half period of an applied electric field, though no coherent signal is found in the SHG experiments. Based on additional electro-optical and dielectric results, the nematic phases are considered to be cybotactic nematic phases with local polar order, and show a dielectric reorientation of the polar domains. Only chiral nematic phases (NcybC *), but not blue phases, are obtained for compounds with one or two chiral (3S)-3,7-dimethyloctyloxy tail(s).

Cybotactic nematic phase in main-chain polyesters with bent-core mesogens

New six main-chain polyesters containing bent-core mesogens with various central units (Ar = 1,2- or 1,3-phenylene and 1,6-, 1,7-, 2,3- or 2,7-naphthylene) were synthesized. All of the polymers were soluble in a mixture of phenol/p-chlorophenol/TCE (25/40/35 w/w/w). The inherent viscosities were in the range of 0.18–0.38 dL/g. Despite the existence of bent-core mesogens eliciting a remarkable diminution of molecular packing, polymer with Ar = 2,7-naphthylene formed a smectic phase, and polymers with both Ar = 1,2-phenylene and 2,3-naphthylene formed nematic phases. Moreover, most of the polymers were distinctly semi-crystalline. Herein, we report our findings regarding the first detection of cybotactic groups from the nematic phases of main-chain polyesters with bent-core mesogens.

Molecular design for a cybotactic nematic phase

We propose two molecular designs for a cybotactic nematic (Ncyb) phase. The U-shaped compound exhibits a skewed Ncyb phase, whereas the rod-like compound possessing a terminal hydroxyl group shows a normal Ncyb phase.

The cybotactic nematic phase of bent-core mesogens: state of the art and future developments.

The molecular clustering observed in the fluid nematic phase of nonlinear liquid crystal molecules underlies exaggerated field effects that portend unique technological advances in next-generation liquid crystal displays. However, the detailed nature of the molecular organization within the clusters and the temporal and spatial persistence of the organization remain unclear. Herein we review the evolution of structural studies of this unique nematic phase. The mounting experimental evidence points to a converging picture of the microscopic nature of this relatively new class of liquid crystals.

Evidence of Cybotactic Order in the Nematic Phase of a Main-Chain Liquid Crystal Polymer with Bent-Core Repeat Unit.

We report the synthesis and structural characterization of a main-chain liquid crystal polymer constituted by a 1,2,4-oxadiazole-based bent-core repeat unit. For the first time, a liquid crystal polymer made of bent mesogenic units is demonstrated to exhibit cybotactic order in the nematic phase. Coupled with the chain-bond constraints, cybotaxis results in maximized molecular correlations that make this material of great potential in the search for the elusive biaxial and ferroelectric nematic phases. Indeed, repolarization current measurements in the nematic phase hint at a ferroelectric-like switching response (upon application of an electric field of only 1.0 V μm-1) that, albeit to be definitely confirmed by complementary techniques, is strongly supported by the comparative repolarization current measurements in the nematic and isotropic phases. Finally, the weak tendency of this polymer to crystallize makes it possible to supercool the cybotactic nematic phase down to room temperature, thus, paving the way for a glassy phase in which the biaxial (and possibly polar) order is frozen at room temperature.

Effect of cybotactic clusters on the elastic and flexoelectric properties of bent-core liquid crystals belonging to the same homologous series

We report results of the splay (K_{11}) and bend (K_{33}) elastic constants and the effective flexoelectric coefficient of three bent-core liquid crystals belonging to a homologous series of 4-cyanoresorcinol bisbenzoates with varying chain lengths. Based on the results of x-ray scattering studies, one of the three compounds with a shorter chain length (C4) has few, if any, clusters present in its nematic phase and behaves quite normally, whereas the others two with longer chain lengths (C6 and C7) show the presence of cybotactic nematic phase with smectic C type clusters. These grow in size with a reduction in temperature. K_{33} is found to be the least for C7, whereas it is weakly dependent on temperature. K_{33} is somewhat higher for C4 and C6 and is almost independent of temperature. K_{11} for C6 and C7 is higher by 20% to 50% than C4 depending on the temperature. K_{11} increases linearly with a reduction in temperature for the three compounds. For C6 K_{11}>K_{33} by a factor up to ∼2 depending on the temperature, for C4 it is greater by a factor up to 1.3, and for C7 it is greater by a factor of ∼2.5. These results suggest that the clusters do not have any effect on K_{11}. The magnitude of the effective flexoelectric coefficient e=(|e_{1}-e_{3}|) is measured by creating a uniform lying helix (ULH) configuration in a planar cell. By doping the bent-core system with a small wt% of a chiral dopant, the ULH is obtained by cooling planar cells to the cholesteric phase under weak electric field. The effective flexoelectric coefficient is greater for the bent-core systems than for calamatics but it is much lower than would otherwise have been expected for such systems. |e_{1}-e_{3}| for C4 > C6 ≈ C7 is greater by 20% to 25% than C6 and C7 at the same reduced temperature. These differences in the effective flexoelectric coefficient can easily arise from a difference in the chain lengths among the members of the series but if the presence of clusters were to have an influence on |e_{1}-e_{3}|, then these would reduce it, contrary to the expectations for the bent-core systems.

Transition between triangular and square tiling patterns in liquid-crystalline honeycombs formed by tetrathiophene-based bolaamphiphiles

A series of 5,5′′′-diphenyl tetrathiophenes with polar glycerol groups at each end and two lateral flexible chains self-assemble into a series of liquid-crystalline honeycombs, formed by the π-conjugated rods which enclose polygonal prismatic cells filled by the lateral chains. With increasing chain length a discontinuous transition from triangular to square honeycombs takes place. At this transition a periodic honeycomb composed of a mixture of square and triangular cells in a ratio 1 : 2 was formed at low temperature, whereas at higher temperature a hexagonal columnar phase composed of triangular and randomly distributed rhombic cells, a new kind of cybotactic nematic phase, and also a cybotactic isotropic phase, both composed of square honeycomb fragments, represent the intermediate states. This provides an example of a dynamic self-assembled system where, depending on the molecular mobility, the transition between two periodic structures with different symmetry either leads to an increase of complexity, or to a chaotic regime with reduced order.

Liquid-crystalline heterodimesogens and ABA-heterotrimesogens comprising a bent 3,5-diphenyl-1,2,4-oxadiazole central unit.

Three new types of terminally connected ABA-heterotrimesogens and heterodimesogens, composed of a bent 3,5-diphenyl-1,2,4-oxadiazole central unit and one or two rod-shaped 4-cyanobiphenyl cores or one 2-phenyl-1,3,4-thiadiazole core, connected by flexible spacers, have been synthesized, and their mesomorphic behavior was studied by optical polarizing microscopy (PM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). All dimesogens exhibit broad ranges of cybotactic nematic phases (NcybA and NcybC), in some cases accompanied by additional mesophases (CybA or SmC) at lower temperature. The combination of the 3,5-diphenyl-1,2,4-oxadiazole unit with one cyanobiphenyl core leads to the removal of tilted smectic and cybotactic nematic phases (SmC, NcybC), which are replaced by the nontilted CybA phases and nematic phases composed of SmA-type clusters (NcybA). The orthogonal cybotactic nematic phases of bent-core mesogens are of special interest for achieving biaxial nematic phases of the orthorhombic type. The orthogonal (NcybA) and skewed (NcybC) cybotactic nematic phases were distinguished by XRD and optical observations.

Extraordinary Magnetic Field Effect in Bent-Core Liquid Crystals

A bent-core mesogen that forms a cybotactic nematic phase exhibits a giant magnetic field-induced shift of its nematic-isotropic and smectic-C-nematic transition temperatures: ΔT(H) = 4 K for H = 10 kOe. In contrast with molecular nematics, in cybotactic nematics the field couples with the anisotropic susceptibility of clusters containing several hundred partially ordered molecules. X-ray diffraction data corroborate a quantitative estimate of inferred cluster size (∼300 molecules). The results represent an unequivocal demonstration of the cluster picture of the nematic phase of this class of nonlinear liquid crystals.

Effects of chain branching and chirality on liquid crystalline phases of bent-core molecules: blue phases, de Vries transitions and switching of diastereomeric states

Bent-core molecules based on a resorcinol bisbenzoate core with a series of distinct substituents in different positions at the central resorcinol core have been synthesized and characterized. The focus is on the effect of branched terminal groups in the racemic and chiral forms on the mesomorphic properties. These were investigated by differential scanning calorimetry, optical polarizing microscopy, X-ray diffraction, electro-optic and dielectric methods. Only bent-core mesogens derived from 4-cyanoresorcinol exhibit liquid crystalline phases and the mesophases of these compounds are strongly influenced by the branching and enantiomeric composition of the terminal chains. Depending on the structure of the rod-like wings and the enantiomeric composition, cybotactic nematic phases (NcybC), BPIII-like isotropic mesophases (BPIIIcybC*) and various polar and apolar smectic phases (SmA, SmC, SmC*, SmCsPA, SmCsPA*) are formed. For one compound, a de Vries type smectic phase is observed and it appears that with decreasing temperature, order develops in two steps. First, at the SmA to SmC transition, the tilt direction becomes long range ordered and in a second step a long range ordering in bend direction takes place. Hence, for the optically active compound a transition from chirality induced polar switching to bend induced (shape induced) antiferroelectricity takes place. In this SmCsPA* phase a homogeneous layer chirality is induced under an applied electric field which interacts with the fixed molecular chirality leading to the energetically favoured diastereomeric state and giving rise to a field direction dependent uniform tilt director orientation. Field reversal induces a flipping of the layer chirality, which first leads to the less favorable diastereomeric state, and then this slowly relaxes to the more stable one by a spontaneous reversal of the tilt direction.

Development of polar order in a bent-core liquid crystal with a new sequence of two orthogonal smectic and an adjacent nematic phase

A 4-cyanoresorcinol based bent-core liquid crystal shows a new phase sequence of two orthogonal smectic phases with short range (SmAPR) and long range (SmAPA) polar order beside a SmA-type cybotactic nematic phase (NCybA), leading to the phase sequence SmAPA–SmAPR–NCybA; this is of importance in LCD technology and provides a significant step forward towards polar and biaxial nematic phases.

Evidence of a polar cybotactic smectic A phase in a new fluorine substituted bent-core compound

The mesomorphic properties of an achiral, fluorine substituted bent-core liquid crystal have been investigated using polarising optical microscopy, electro-optics, X-ray diffraction and dielectric spectroscopy. A new phase, designated as CybAPA, has been found. This phase is a cluster phase consisting of microscopic enlarged antiferroelectric smectic A type clusters. The CybAPA phase is observed below a SmA phase and exists irrespective of the alignment layer and the cell thickness. The CybAPA phase behaves like a nematic phase with low viscosity and exhibits thermal fluctuations. But on applying an electric field, it shows smectic-like textures and exhibits tristable antiferroelectric switching. X-Ray diffraction of aligned samples of this phase confirms the non-tilted orientation of the major director and long range 1D positional order of the molecules. The dielectric spectroscopic studies show the appearance of strong dipolar correlations on approaching the CybAPA phase from the higher temperature SmA phase, confirming the formation of SmAPA clusters, which is associated with the onset of phase biaxiality. This provides a significant step forward to achieve the illusive orthorhombic biaxial cybotactic nematic phase from bent-core molecules.

Nematic phases of bent-core mesogens

Bent-core mesogens derived from 4-cyanoresorcinol with terminal alkyl chains have been synthesized and investigated by polarizing microscopy, XRD and electro-optical methods. Short chain compounds have exclusively nematic phases which can be cooled to ambient temperature. These nematic phases are similar to ordinary nematic phases with only nearest neighbour correlation (N) whereas long chain compounds form SmC-type cybotactic clusters and these cybotactic nematic phases (NcybC) can be regarded as strongly fragmented SmC phases. The chain length dependent as well as temperature dependent structural transition from N to NcybC is continuous and associated with a change of the position and intensity of the small angle scattering in the XRD patterns. Moreover, a temperature dependent stepwise transition from cybotactic nematic phases to different types of non-polar and tilted smectic phases (SmC(I) and SmC(II)) is observed with a mesophase composed of elongated, but not yet fused cybotactic clusters (CybC) as an intermediate state of this transition. This improves the understanding of the nature and special properties of the nematic phases formed by bent-core molecules as well as their transition to smectic phases and it paves the way to new materials with spontaneous or field-induced biaxial nematic phases at ambient temperatures.