Flexoelectric polarization studies in bent-core nematic liquid crystals.

The flexoelectric polarization (Pf) of four bent-core nematic liquid crystals (LCs) has been measured using the pyroelectric effect. Hybrid aligned nematic cells are fabricated for measuring the pyroelectric response over the entire range of the nematic phase. It is found that the magnitude of flexoelectric polarization Pf and the sum of the flexoelectric coefficients |e1+e3| for the bent-core LCs studied here are three to six times higher than for the calamitics. Pf is found to depend on the transverse dipole moment of LC molecules. However, |e1+e3| values are by no means giant as |e3| alone had been reported for a bent-core nematic system previously. The dependence of the sum of "splay and bend flexoelectric coefficients" is discussed in terms of the shape of the molecule and of the dipole moment directed normal to the molecular axis.

Dielectric and electro-optic studies of a bimesogenic liquid crystal composed of bent-core and calamitic units.

A bimesogen, BR1, composed of a bent-core and calamitic unit, linked laterally via a flexible spacer is investigated by dielectric and electro-optic techniques. X-ray results show the presence of clusters in the nematic phase, and the cluster size is of the order of the thickness of a single layer. The splitting of the small-angle scattering Δχ/2 is about 50°, which indicates SmC like clusters with a significant tilt of the molecules in the quasilayers. The sign reversal of the dielectric anisotropy Δε' is observed as a function of frequency; the behavior is rather similar to that exhibited by the conventional dual frequency nematics, composed of a calamitic mesogen, with the exception that it occurs at much lower frequencies in this material. Interestingly, as the bimesogen enters its nematic phase, the average permittivity decreases as the temperature is lowered. This indicates the onset of antiparallel association of some of the dipoles in the system, and this type of association is much more prominent in BR1 in comparison to other bent-core liquid crystalline systems composed of the same bisbenzoate core unit. The analysis of the dielectric spectra using the Maier-Meier model confirms the onset of an antiparallel correlation of dipoles occurring at the isotropic to nematic phase transition temperature. Additionally these results support a model of the cluster where the transverse dipole moments in the neighboring layers are antiparalleled to each other.

Spontaneous and field-induced mesomorphism of a silyl-terminated bent-core liquid crystal as determined from second-harmonic generation and resonant X-ray scattering.

The polarity and structure of the phases of a liquid crystal constituted by thiophene-based bent-core molecules is investigated by means of optical second-harmonic generation (SHG), and resonant and conventional X-ray diffraction. The material studied is representative of a wide family of mesogens that contain silyl groups at the ends of the chains. These bulky terminal groups have been reported to give rise to smectic phases showing ferroelectric switching. However, the analysis of the SHG signal before and after application of electric fields has allowed us to establish unambiguously that the reported ferroelectricity is not intrinsic to the material but stabilized by the cell substrates once an electric field has been applied. In addition, the results obtained from resonant X-ray diffraction indicate that virgin samples have antiferroelectric undulated synclinic smectic structures.

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.

Biaxial order parameter in the homologous series of orthogonal bent-core smectic liquid crystals.

The fundamental parameter of the uniaxial liquid crystalline state that governs nearly all of its physical properties is the primary orientational order parameter (S) for the long axes of molecules with respect to the director. The biaxial liquid crystals (LCs) possess biaxial order parameters depending on the phase symmetry of the system. In this paper we show that in the first approximation a biaxial orthogonal smectic phase can be described by two primary order parameters: S for the long axes and C for the ordering of the short axes of molecules. The temperature dependencies of S and C are obtained by the Haller's extrapolation technique through measurements of the optical birefringence and biaxiality on a nontilted polar antiferroelectric (Sm-AP(A)) phase of a homologous series of LCs built from the bent-core achiral molecules. For such a biaxial smectic phase both S and C, particularly the temperature dependency of the latter, are being experimentally determined. Results show that S in the orthogonal smectic phase composed of bent cores is higher than in Sm-A calamatic LCs and C is also significantly large.

Complex tiling patterns in liquid crystals.

In this account recent progress in enhancing the complexity of liquid crystal self-assembly is highlighted. The discussed superstructures are formed mainly by polyphilic T-shaped and X-shaped molecules composed of a rod-like core, tethered with glycerol units at both ends and flexible non-polar chain(s) in lateral position, but also related inverted molecular structures are considered. A series of honeycomb phases composed of polygonal cylinders ranging from triangular to hexagonal, followed by giant cylinder honeycombs is observed for ternary T-shaped polyphiles on increasing the size of the lateral chain(s). Increasing the chain size further leads to new modes of lamellar organization followed by three-dimensional and two-dimensional structures incorporating branched and non-branched axial rod-bundles. Grafting incompatible chains to opposite sides of the rod-like core leads to quaternary X-shaped polyphiles. These form liquid crystalline honeycombs where different cells are filled with different material. Projected on an Euclidian plane, all honeycomb phases can be described either by uniformly coloured Archimedean and Laves tiling patterns (T-shaped polyphiles) or as multi-colour tiling patterns (X-shaped polyphiles). It is shown that geometric frustration, combined with the tendency to segregate incompatible chains into different compartments and the need to find a periodic tiling pattern, leads to a significant increase in the complexity of soft self-assembly. Mixing of different chains greatly enhances the number of possible 'colours' and in this way, periodic structures comprising up to seven distinct compartments can be generated. Relations to biological self-assembly are discussed shortly.

Flexoelectric measurements of a bent-core nematic liquid crystal.

A large flexoelectric polarization might be expected for a bent-core nematic liquid crystal, due to the combination of molecular shape and transverse dipole component. In this study a bent-core nematic compound is doped to be highly chiral, and measurements of the difference in flexoelectric coefficients (e(1)-e(3)) are carried out by exploiting the chiral flexoelectro-optic effect. The measured flexoelectric coefficients are greater than those for many conventional calamitic nematics, but several orders of magnitude lower than recent reports on other bent-core compounds. The influence of the bent molecular shape on the nematic phase is evident from measurements of the elastic constants, where an unusually low ratio of k(3) to k(1) indicates that bend distortions of the director are relatively lower in energy compared to those involving splay.

Short-range correlations seen in the nematic phase of bent-core liquid crystals by dielectric and electro-optic studies.

Three bent-core nematic liquid crystals having the same core but with different terminal groups, short (C4) and long (C7,C9) tails, are investigated by dielectric and electro-optic contrast spectroscopic techniques. C4 shows sign reversal in the dielectric anisotropy Δε' as a function of both temperature and frequency, whereas C9 shows only negative Δε' in the entire mesophasic region. The behavior of C7 is intermediate of the two. Results of a dielectric study show that both C7 and C9 exhibit strong short-range polar correlations normal to the director. The correlation lengths of these interactions are found to be similar to those from the x-ray scattering. An increased hindered rotation for C9 compared to C4 moves the dielectric dispersion for ε(|') to much lower frequencies, such that C9 shows only negative Δε' over the entire temperature range.

Sequence of four orthogonal smectic phases in an achiral bent-core liquid crystal: evidence for the SmAP(α) phase.

The mesomorphic properties of an achiral bent-core liquid crystal derived from 4-cyanoresorcinol are studied by polarizing optical microscopy, x-ray diffraction, and second harmonic electro-optic response. It shows a novel sequence of four nontilted or orthogonal smectic phases on cooling: SmA-SmAP(R)-SmAP(X)-SmAP(A). Here SmAP(X) is the new orthogonal polar uniaxial smectic phase. The electric-field-induced transformations in the SmAP(X) phase give rise to two biaxial states separated by a uniaxial one. The second harmonic electro-optic response in this phase is interpreted in terms of the polar interaction with the electric field. A comparison of the experimental results with the next-nearest-neighbor model for the structure of the SmAP(X) phase shows it to be an SmAP(α) phase.

Spontaneously chiral domains of an achiral bent-core nematic liquid crystal in a planar aligned device.

An achiral fixed bent-core nematic liquid crystal in an antiparallel aligned planar device is observed to form three distinct domains. Regions are observed which are achiral planar, as well as domains displaying both positive and negative chirality that are stable over a significant temperature interval. In such a device the presence of spontaneous positive and negatively twisted domains is highly unusual. By studying the electro-optics of the device relevant director structures are inferred, and it is additionally found that a sufficiently large applied electric field will drive the chiral domains into the achiral state.

Chiral isotropic liquids from achiral molecules.

A variety of simple bent-core molecules exhibit smectic liquid crystal phases of planar fluid layers that are spontaneously both polar and chiral in the absence of crystalline order. We found that because of intralayer structural mismatch, such layers are also only marginally stable against spontaneous saddle splay deformation, which is incompatible with long-range order. This results in macroscopically isotropic fluids that possess only short-range orientational and positional order, in which the only macroscopically broken symmetry is chirality--even though the phases are formed from achiral molecules. Their conglomerate domains exhibit optical rotatory powers comparable to the highest ever found for isotropic fluids of chiral molecules.

Influence of the core structure on the development of polar order and superstructural chirality in liquid crystalline phases formed by silylated bent-core molecules: lateral substituents.

The influence of lateral substituents was studied for a new series of bent-core liquid crystals with heptamethyltrisiloxane units at both ends of the aliphatic side chains. These materials were investigated by polarized light microscopy, differential scanning calorimetry, X-ray scattering and electro-optical methods. An antiferroelectric switching columnar phase was found for the non-substituted compound. Different types of non-switching columnar phases were obtained for molecules having substituents (CH, NO) in the bay position, whereas a temperature-dependent transition from polar to non-polar smectic phases was found for molecules having substituents (Cl, CN) adjacent to one of the ester linking units. For the CN-substituted compound a new phase sequence SmCP-SmC-Cub-Iso was observed. The occurrence of the cubic phase is associated with a steric frustration due to the bulky silyl groups. The special rectangular columnar mesophase of the nitro-substituted compound is discussed with respect to its relation to B7-type mesophases.

Fluorescent J-type aggregates and thermotropic columnar mesophases of perylene bisimide dyes.

A series of perylene tetracarboxylic acid bisimides 3a-e bearing 3,4,5-tridodecyloxyphenyl substituents on the imide N atoms and zero, two, or four phenoxy-type substituents in the bay positions of the perylene core were synthesized. From investigations of their spectroscopic properties and aggregation behavior in low-polarity solvents by absorption and fluorescence optical spectroscopy, not only were these compounds found to form fluorescent J-type aggregates, but also binding constants for aggregation could be derived which reflect the number and steric demand of the phenoxy substituents for bisimides 3a-d. In the pristine state, 3a-d form thermotropic hexagonal columnar mesophases which exist over a broad temperature range from below -30 degrees C to over 300 degrees C. For the tetraphenoxy-substituted compound 3e, however, a layered crystalline structure was found. This difference in behavior can be explained by the concept of microphase segregation of the aromatic cores of the molecules and the alkyl chains at the periphery. The high stability and bright fluorescence of the mesophase of several of the compounds make them promising for applications as polarizers or components in (opto)electronic devices.

Hydrogen bond directed formation of liquid-crystalline merocyanine dye assemblies.

Combined interaction of triple hydrogen bonding, dipolar pi-pi aggregation and micro-segregation in a melamine-barbituric acid dye assembly leads to a columnar mesophase which could be characterized by optical polarising microscopy, differential scanning calorimetry and X-ray diffraction.

Thermotropic and lyotropic liquid crystalline phases of rigid aromatic amphiphiles

Rodlike amphiphilic molecules that contain exclusively aromatic building-blocks and no flexible alkyl chains have been synthesized and their mesomorphic properties investigated. These novel compounds bear diol head groups of different size (2,3-dihydroxypropyloxy or 5,6-dihydroxy-3-oxahexyloxy groups) at one end of a biphenyl unit, various aromatic segments (benzyloxy, 4-, 3-, or 2-methylbenzyloxy, phenoxy groups) at the other, and additional methyl substituents in different positions. They were synthesized by using Suzuki cross-coupling reactions as the key steps. Their thermotropic mesomorphism was investigated by means of polarized light optical microscopy, differential scanning calorimetry, and, for enantiotropic phases, by X-ray scattering. The liquid crystallinity of this class of compounds is influenced by protic solvents, such as water and glycerol. Dependent on the temperature and the solvent content, different SA phases were found. Several mesophases resulting from the frustration of these layer structures (e.g., different columnar phases, optical isotropic mesophases, and nematic phases) were also present. The smectic phases have different degrees of intercalation (SAd, SA2). The columnar phases are supposed to be ribbon structures that result from the collapse of the smectic layers. They occur in some pure compounds or they are induced upon the addition of protic solvents. The particular phase sequences of the different compounds depend mainly on the position of the methyl substituents at the biphenyl cores and are largely determined by the degree of intercalation of the aromatic cores.

Molecular Design of Liquid-Crystalline Block Molecules: Semifluorinated Pentaerythritol Tetrabenzoates Exhibiting Lamellar, Columnar, and Cubic Mesophases.

Fluid assemblies of star-shaped molecules like 1 form a range of thermotropic liquid crystalline phases, and represent a borderline case between anisometric mesogens, surfactants, and block copolymers. The low molecular mass molecules (<5.5 kDa) consist of a semipolar central core and a shell of semifluorinated chains.

A double mesogen based on linked p-terphenyl units.

The structure of bis(4,4"-decyloxy-p-terphenyl-2'-ylmethyl) carbonate, C(79)H(110)O(7), (I), has been determined at 123 K. It is a new type of twin mesogen. No two adjacent aromatic rings are coplanar and the four decyloxy side chains are maximally extended. Molecules of the compound are packed along the crystallographic a axis. The molecular arrangement is a precursor of a smectic A phase.

Design of new mesogenic block molecules: formation of columnar mesophases by calamitic bolaamphiphiles with lateral lipophilic substituents.

Rigid bolaamphiphiles with lateral alkyl chains such as 1 form columnar mesophases of a novel type based on microsegregation of the three incompatible parts of the molecules (shown schematically).