Twist-bend Phase Research Articles

Miscibility Studies of Bismesogen CBnCB Forming Nematic Twist-Bend Phase with Cyanobiphenyls nCB.

This work aims to determine how the nematic twist-bend phase (NTB) of bismesogens containing two rigid parts of cyanobiphenyls connected with a linking chain containing n = 7, 9, and 11 methylene groups behaves in mixtures with structurally similar cyanobiphenyls nCB, n = 4-12, 14. The whole phase diagrams are presented for the CB7CB-nCB system. For the other systems, CB9CB-nCB and CB11CB-nCB, only curves corresponding to NTB-N phase transition are presented. Based on the temperature-concentration range of the existence of NTB phase, it was established that an increase in the alkyl chain length of CBnCB causes an increase in the stability of the NTB phase. But surprisingly, an increase in the alkyl chain length of nCB compounds does not change the slope of the NTB-N equilibrium line on phase diagrams. It is slightly bigger when the nCB compound has the same length of alkyl chain as the length of the linking group of a bismesogen. XRD studies were carried out for two mixtures.

Double-Helical Tiled Chain Structure of the Twist-Bend Liquid Crystal Phase in CB7CB

The twist-bend nematic liquid crystal phase is a three-dimensional fluid in which achiral bent molecules spontaneously form an orientationally ordered, macroscopically chiral, heliconical winding of a ten nanometer-scale pitch in the absence of positional ordering. Here, the structure of the twist-bend phase of the bent dimer CB7CB and its mixtures with 5CB is characterized, revealing a hidden invariance of the self-assembly of the twist-bend structure of CB7CB, such that over a wide range of concentrations and temperatures, the helix pitch and cone angle change as if the ground state for a pitch of the TB helix is an inextensible heliconical ribbon along the contour formed by following the local molecular long axis (the director). Remarkably, the distance along the length for a single turn of this helix is given by 2πRmol, where Rmol is the radius of bend curvature of a single all-trans CB7CB molecule. This relationship emerges from frustrated steric packing due to the bent molecular shape: space in the fluid that is hard to fill attracts the most flexible molecular subcomponents, a theme of nanosegregation that generates self-assembled, oligomer-like correlations of interlocking bent molecules in the form of a brickwork-like tiling of pairs of molecular strands into duplex double-helical chains. At higher temperatures in the twist-bend phase, the cone angle is small, the director contour is nearly along the helix axis z, and the duplex chains are sequences of biaxial elements formed by overlapping half-molecule pairs, with an approximately 45° rotation of the biaxis between each such element along the chain.

Liquid Crystal Dimers and the Twist-Bend Phases: Non-Symmetric Dimers Consisting of Mesogenic Units of Differing Lengths.

The syntheses and characterisation of the 4-[{[4-({n-[4-(4-cyanophenyl)phenyl]-n-yl}oxy)phenyl]-methylidene}amino]phenyl-4-alkoxybenzoates (CBnOIBeOm) are reported with n=8 and 10 and m=1-10. The two series display fascinating liquid crystal polymorphism. All twenty reported homologues display an enantiotropic nematic (N) phase at high temperature. When the length of the spacer (n) is greater than that of the terminal chain (m), the twist-bend nematic (NTB) phase is observed at temperatures below the N phase. As the length of the terminal chain is increased and extends beyond the length of the spacer up to three smectic phases are observed on cooling the N phase. One of these smectic phases has been assigned as the rare twist-bend smectic C subphase, the SmCTB-α phase. In all the smectic phases, a monolayer packing arrangement is seen, and this is attributed to the anti-parallel associations of the like mesogenic units.

Theoretical models for the nematic twist-bend phase and the Landau de Gennes theory of Longa and Tomczyk

ABSTRACT We present a critical analysis of the existing phenomenological theories of the nematic twist-bend phase including the models proposed by Dozov and Selinger and the more general Landau de Gennes theory of L. Longa and W. Tomczyk. The role of the flexoelectric polarisation is considered in detail as well as the stabilisation of the nanoscale helical structure of the twist-bend phase. In particular we focus into the mechanism of the reduction of the bend elastic constant determined by negative flexoelectric corrections and discuss why the splay elastic constant is not reduced at all. A molecular theory of elasticity of bent-core nematics, which also enables one to describe the reduction of the bend elastic constant, is considered in detail as well. Finally we consider two different tensor orientational order parameters of the twist-bend phase which describe all kinds of uniaxial and local biaxial ordering of bent-core molecules in the twist-bend phase.

Dielectric Study of Liquid Crystal Dimers: Probing the Orientational Order and Molecular Interactions in Nematic and Twist-Bend Nematic Phases.

Dielectric spectroscopy in frequencies that range from 10 Hz to 1 GHz has been used to study the molecular orientational dynamics of the two types of dimers that form the twist-bend nematic phase over a wide range of temperatures for both nematic and twist-bend nematic phases. The symmetrical and asymmetrical liquid crystal dimers with the cyanobiphenyl mesogenic groups were investigated. The results were analyzed within the framework of the molecular theory of dielectric permittivity for nematogens. The two molecular processes can be assigned to the reorientation of the monomeric unit: the high frequency one to the precessional rotation of the longitudinal components of the cyanobiphenyl groups (CN) and the second (low frequency) to the end-over-end rotation of the CN dipole around the short molecular axis. The precession mode, which is determined by the local order and is almost unaffected by the phase transition from the nematic to the twist-bend phase, while the end-over-end rotation clearly slowed down at the transition, as it is affected by the growth of the intermolecular interactions. The latter corresponds well to the fact revealed by IR spectroscopy about the longitudinal correlation of the molecular dipoles.

How Do Intermolecular Interactions Evolve at the Nematic to Twist-Bent Phase Transition?

Polarized beam infrared (IR) spectroscopy provides valuable information on changes in the orientation of samples in nematic phases, especially on the role of intermolecular interactions in forming the periodically modulated twist–bent phase. Infrared absorbance measurements and quantum chemistry calculations based on the density functional theory (DFT) were performed to investigate the structure and how the molecules interact in the nematic (N) and twist–bend (NTB) phases of thioether dimers. The nematic twist–bend phase observed significant changes in the mean IR absorbance. On cooling, the transition from the N phase to the NTB phase was found to be accompanied by a marked decrease in absorbance for longitudinal dipoles. Then, with further cooling, the absorbance of the transverse dipoles increased, indicating that transverse dipoles became correlated in parallel. To investigate the influence of the closest neighbors, DFT calculations were performed. As a result of the optimization of the molecular cores system, we observed changes in the square of the transition dipoles, which well corresponds to absorbance changes observed in the IR spectra. Interactions of molecules dominated by pairing were observed, as well as the axial shift of the core to each other.

Nematic twist-bend phase of a bent liquid crystal dimer: field-induced deformations of the helical structure and macroscopic polarization

The twist-bend nematic (Ntb) phase is a recent addition to the family of nematic (N) phases of liquid crystals (LCs). A net polar order in the Ntb phase under an external electric field is interesting and it was predicted in several recent theoretical studies. We investigated the field-induced polarization behaviour, dielectric, and electro-optic properties of a bent LC dimer CB7CB in the N and Ntb phases. A threshold-dependent polarization current response was obtained in both the phases under triangular and square-wave input electric fields, existing till frequencies as high as 150 Hz. The polarization switching times were found in ∼1 ms region, especially in the N phase. In the Ntb phase, electric field-induced deformation of the helical structure was observed, like ferroelectric LCs. Dielectric measurements revealed the presence of cybotactic clusters via collective relaxations. The dielectric anisotropy (Δϵ) is negative at the frequencies of polarization measurements. The net polarization resulted from field-induced reorientation of cybotactic clusters and additionally from the field-induced deformation of helical structures in the Ntb phase. We explored the possibility of ionic contributions to the net polarization by synthesizing TiO2 nanoparticles (NPs) dispersed CB7CB LC nanocomposite. Incorporation of the NPs resulted in reduction of the collective order, increase in the ionic impurity content and conductivity, but an extinction of the field-induced polarization response. Our results demonstrate that the net polarization has competing contributions from both ferroelectric-like and ionic origin (up to ∼10 Hz) in the LC phases, but it becomes dominantly ferroelectric-like at higher frequencies.

Study of the Experimental and Simulated Vibrational Spectra Together with Conformational Analysis of Thioether Cyanobiphenyl-Based Liquid Crystal Dimers.

Infrared spectroscopy (IR) and quantum chemistry calculations that are based on the density functional theory (DFT) have been used to study the structure and molecular interactions of the nematic and twist-bend phases of thioether-linked dimers. Infrared absorbance measurements were conducted in a polarized beam for a homogeneously aligned sample in order to obtain more details about the orientation of the vibrational transition dipole moments. The distributions to investigate the structure and conformation of the molecule dihedral angle were calculated. The calculated spectrum was compared with the experimental infrared spectra and as a result, detailed vibrational assignments are reported.

Anatomy of a Discovery: The Twist–Bend Nematic Phase

New fluid states of matter, now known as liquid crystals, were discovered at the end of the 19th century and still provide strong themes in scientific research. The applications of liquid crystals continue to attract attention, and the most successful so far has been to the technology of flat panel displays; this has diversified in recent years and LCDs no longer dominate the industry. Despite this, there is plenty more to be uncovered in the science of liquid crystals, and as well as new applications, novel types of liquid crystal phases continue to be discovered. The simplest liquid crystal phase is the nematic together with its handed or chiral equivalent, named the cholesteric phase. In the latter, the aligned molecules of the nematic twist about an axis perpendicular to their alignment axis, but in the 1970s a heliconical phase with a tilt angle of less than 90° was predicted. The discovery of this phase nearly 40 years later is described in this paper. Robert Meyer proposed that coupling between a vector order parameter in a nematic and a splay or bend elastic distortion could result in spontaneously splayed or bent structures. Later, Ivan Dozov suggested that new nematic phases with splay–bend or twist–bend structures could be stabilised if the appropriate elastic constants became negative. Theoretical speculation on new nematic phases and the experimental identification of nematic–nematic phase transitions are reviewed in the paper, and the serendipitous discovery in 2010 of the nematic twist–bend phase in 1″,7″-bis(4-cyanobiphenyl-4′-yl)heptane (CB7CB) is described.

Coupling between splay deformations and density modulations in splay-bend phases of bent colloidal rods.

Using a grand-canonical Landau-de Gennes theory for colloidal suspensions of bent (banana-shaped) rods, we investigate how spatial deformations in the nematic director field affect the local density of twist-bend and splay-bend nematic phases. The grand-canonical character of the theory naturally relates the local density to the local nematic order parameter S. In the splay-bend phase, we find S and hence the local density to modulate periodically along one spatial direction. As a consequence the splay-bend phase has the key symmetries of a smectic rather than a nematic phase. By contrast we find that S and hence the local density do not vary in space in the twist-bend phase, which is therefore a proper nematic phase. The theoretically predicted one-dimensional density modulations in splay-bend phases are in agreement with recent simulations.

Skyrmion tubes in achiral nematic liquid crystals.

We analyze the interaction with uniform external fields of nematic liquid crystals within a recent generalized free energy posited by Virga and falling in the class of quartic functionals in the spatial gradients of the nematic director. We review some known interesting solutions, i.e., uniform heliconical structures, which correspond to the so-called twist-bend nematic phase and we also study the transition between this phase and the standard uniform nematic one. The twist-bend phase is further reproduced by three-dimensional simulations. Moreover, we find liquid crystal configurations, which closely resemble some novel, experimentally detected, structures called Skyrmion tubes. Skyrmion tubes are characterized by a localized cylindrically symmetric pattern surrounded by either twist-bend or uniform nematic phase. We study the equilibrium differential equations and find numerical solutions and analytical approximations.

The Magic 4-Cyanoresocinols - Their Role in the Understanding of Phenomena at the Rod-Banana Cross-Over and Relations to Twist-Bend Phases and Other Newly Emerging LC Phase Types

ABSTRACT In this account, bent-core molecules involving the polar cyano-group are reviewed with a focus on the intensely investigated class of 4-cyanoresorcinol bisbenzoates. Cybotaxis and phase biaxiality of their nematic phases, the transition from nematic to smectic phases and the development of tilt and polar order in their smectic phases are discussed. Of special interest are heliconical (twist–bend) smectic intermediate phases occurring at the transition from paraelectric to antiferroelectric polar smectic phases if coinciding with the transition between anticlinic and synclinic tilt correlation. For some compounds, a reentrant polar SmA phase (SmALTPF) is observed below SmC and a silylated compound forms a new leaning-type phase. The formation of these achiral phases instead of the polar SmC phases involving layer chirality is discussed under the aspect of enantiophobic vs. enantiophilic organization. The effects of core structure and chain branching and, in addition, the effects of the intrinsic transient molecular, superstructural, and permanent molecular chirality on LC self-assembly are discussed.

Twist-bend nematics and heliconical cholesterics: a physico-chemical analysis of phase transitions and related specific properties

ABSTRACT Certain nematic liquid crystals, for example, those formed by banana-shaped molecules, can exhibit a low-temperature twist-bend nematic (Ntb) phase. Upon addition of chiral dopants, a chiral version of the twist-bend phase (N*tb) can be observed below the conventional chiral nematic (N*) phase, while under electric field the N* phase is transformed into a specific state known as ‘oblique helicoidal cholesteric’. In this work, we have studied the well-known Ntb-forming system CB7CB:CB6OCB with addition of 5CB and chiral dopants (ChDs) using optical microscopy, differential scanning calorimetry (DSC), and measurements of temperature-dependent optical transmission using optical microscopy. Effects of 5CB and different chiral dopants (of steroid or non-steroid nature) upon thermal stability of Ntb phase were analysed, and selective reflection in the visible range could be observed in the N* phase with a sufficiently high ChD content. As a peculiar feature, sharp unwinding of the cholesteric helix was observed at lower temperatures when approaching the N*tb phase, which appears to be similar to the helix unwinding close to the smectic-A transition.

A generalized density-modulated twist-splay-bend phase of banana-shaped particles

In 1976, Meyer predicted that bend distortions of the nematic director field are complemented by deformations of either twist or splay, yielding twist-bend and splay-bend nematic phases, respectively. Four decades later, the existence of the splay-bend nematic phase remains dubious, and the origin of these spontaneous distortions uncertain. Here, we conjecture that bend deformations of the nematic director can be complemented by simultaneous distortions of both twist and splay, yielding a twist-splay-bend nematic phase. Using theory and simulations, we show that the coupling between polar order and bend deformations drives the formation of modulated phases in systems of curved rods. We find that twist-bend phases transition to splay-bend phases via intermediate twist-splay-bend phases, and that splay distortions are always accompanied by periodic density modulations due to the coupling of the particle curvature with the non-uniform curvature of the splayed director field, implying that the twist-splay-bend and splay-bend phases of banana-shaped particles are actually smectic phases.

The role of intermolecular interactions in stabilizing the structure of the nematic twist-bend phase.

The understanding of the relationship between molecular structure and the formation of the nematic twist-bend phase is still at an early stage of development. This is mainly related to molecular geometry, while the correlation between the nematic twist-bend phase and the electronic structure is ambiguous. To explore the electronic effect on properties and stabilization of the nematic twist-bend phase we investigated 2′,3′-difluoro-4,4′′-dipentyl-p-terphenyl dimers (DTC5Cn). We used polarized fourier transform infrared spectroscopy, which can, at least in principle, provide information about the ordering in the twist-bend phase. All dimers show a significant drop in the average value of the transition dipole moment for parallel dipoles at the transition from the nematic to the twist-bend phase, and an increase for perpendicular dipoles, despite remaining unchanged for the monomer. Density functional theory calculations were used to determine the geometric and electronic properties of the hydrogen bonded complexes. We have provided experimental and theoretical evidence of stabilization of the nematic twist-bend phase by arrays of multiple hydrogen bonds (XF⋯HX, X–benzene ring).

Molecular biaxiality determines the helical structure - infrared measurements of the molecular order in the nematic twist-bend phase of difluoro terphenyl dimer.

Fourier-transform infrared polarized spectroscopy was employed, to obtain the three components of the infrared absorbance for a series of bent-shaped dimers containing double fluorinated terphenyl core (DTC5Cn, n = 5, 7, 9, 11). The data were used to calculate both uniaxial and biaxial order parameters, for various molecular groups of dimers. The molecule bend was estimated based on the observed differences between the uniaxial order parameters for the terphenyl core and central hydrocarbon linker. The orientational order, distinctly reverses its monotonic trend of increase to decrease at the transition temperature, from the uniaxial nematic to the twist-bend nematic phase as result of the director tilt in latter/(twist-bend) phase. The molecular biaxiality, which is negligible in the nematic phase, starts increasing on entering the twist-bend nematic phase, following a sin-square relationships with the tilt angle. The local director curvature is found to be controlled by the molecular biaxiality parameter.

Chemical-Physical Characterization of a Binary Mixture of a Twist Bend Nematic Liquid Crystal with a Smectogen

Nematic twist-bend phases (NTB) are new types of nematic liquid crystalline phases with attractive properties for future electro-optic applications. However, most of these states are monotropic or are stable only in a narrow high temperature range. They are often destabilized under moderate cooling, and only a few single compounds have shown to give room temperature NTB phases. Mixtures of twist-bend nematic liquid crystals with simple nematogens have shown to strongly lower the nematic to NTB phase transition temperature. Here, we examined the behaviour of new types of mixtures with the dimeric liquid crystal [4′,4′-(heptane-1,7-diyl)bis(([1′,1″-biphenyl]4″-carbo-nitrile))] (CB7CB). This now well-known twist-bend nematic liquid crystal presents a nematic twist-bend phase below T ≈ 104 °C. Mixtures with other monomeric alkyl or alkoxy -biphenylcarbonitriles liquid crystals that display a smectic A (SmA) phase also strongly reduce this temperature. The most interesting smectogen is 4′-Octyl-4-biphenylcarbonitrile (8CB), for which a long-term metastable NTB phase is found at room and lower temperatures. This paper presents the complete phase diagram of the corresponding binary system and a detailed investigation of its thermal, optical, dielectric, and elastic properties.

Temperature dependence of bend elastic constant in oblique helicoidal cholesterics

Elastic moduli of liquid crystals, known as Frank constants, are of quintessential importance for understanding fundamental properties of these materials and for the design of their applications. Although there are many methods to measure the Frank constants in the nematic phase, little is known about the elastic constants of the chiral version of the nematic, the so-called cholesteric liquid crystal, since the helicoidal structure of the cholesteric renders these methods inadequate. Here we present a technique to measure the bend modulus K33 of cholesterics that is based on the electrically tunable reflection of light at an oblique helicoidal ChOH cholesteric structure. K33 is typically smaller than 0.6 pN, showing a nonmonotonous temperature dependence with a slight increase near the transition to the twist-bend phase. K33 depends strongly on the molecular composition. In particular, chiral mixtures that contain the flexible dimer 1′′,7′′-bis(4-cyanobiphenyl-4′-yl) heptane (CB7CB) and rodlike molecules such as pentylcyanobiphenyl (5CB) show a K33 value that is 5 times smaller than K33 of pure CB7CB or of mixtures of CB7CB with chiral dopants. Furthermore, K33 in CB11CB doped with a chiral agent is noticeably smaller than K33 in a similarly doped CB7CB which is explained by the longer flexible link in CB11CB. The proposed technique allows a direct in-situ determination of how the molecular composition, molecular structure and molecular chirality affect the elastic properties of chiral liquid crystals.

Coarse-grained model of the nematic twist-bend phase from a stable state elastic energy.

The twist-bend nematic (N_{TB}) phase is a doubly degenerated heliconical structure with nanometric pitch and spontaneous bend and twist deformations. It is favored by symmetry-breaking molecular structures, such as bent dimers and bent-core molecules, and it is currently one of the burgeoning fields of liquid-crystal research. Although tremendous advances have been reported in the past five years, especially in molecular synthesis, most of its potential applications are held back by the lack of a proper and definitive elastic model to describe its behavior under various situations such as confinement and applied field. In this work we use a recently proposed stable state elastic model and the fact that the mesophase behaves as a lamellar structure to propose a mesoscopic or coarse-grained model for the N_{TB} phase. By means of standard procedures used for smectic and cholesteric liquid crystals, we arrive at a closed-form energy for the phase and apply it to a few situations of interest. The predicted compressibility for several values of the cone angle and the critical field for field-induced deformation agree well with recent experimental data.

The twist-bend phases: structure–property relationships, chirality and hydrogen-bonding

ABSTRACT This article will review some of our recent work concerning the relationships between molecular structure and the observation of the fascinating twist-bend nematic, NTB, phase. From a chemist’s perspective, understanding the molecular features influencing the formation and stabilisation of the NTB phase is of paramount importance, and allows for the design of new materials that have targeted properties. As such, recent work in Aberdeen has had the primary aim of enhancing our current understanding of these relationships in dimeric liquid crystals, through the synthesis and characterisation of a diverse range of materials, including a selection of supramolecular liquid crystals. A second aim has been to explore the intriguing question as to how the NTB phase, having spontaneous structural chirality, would respond at a microscopic level to the presence of intrinsic molecular chirality – the inclusion of chiral fragments in the dimers – and to obtain examples of the ‘chiral’ twist-bend nematic phase (N*TB) for comparative study alongside the conventional NTB phase. We also show that bent achiral molecules form heliconical smectic phases, as predicted by Dozov in his seminal 2001 work.