Bent-core Materials Research Articles

The synthesis, mesomorphic and dielectric investigation of new unsymmetrical bent-core mesogens derived from 3-hydroxybenzoic acid

The synthesis, mesomorphic and dielectric investigation of new unsymmetrical bent-core mesogens derived from 3-hydroxybenzoic acid central core with linked two rodlike units carrying (S)-3,7-dimethyloctyloxy group and an n-alkyloxy chain at both terminals are presented. The liquid crystalline properties of the new unsymmetrical bent-core materials have been investigated by polarizing optical microscopy and differential scanning calorimetry. New compounds with the reversed ester linking unit exhibit a monotropic or enantiotropic columnar mesophase at lower temperatures as compared to analogs with a straight chain depending on the presence of the branched (S)-3,7-dimethyloctyloxy terminal chain. Dielectric measurements for one of the bent-core mesogens, 3-[[4-[[4-(octyloxy)benzoyl]oxy]benzoyl]oxy]benzoic acid 4-[[4-((S)-3,7-dimethyloctyloxy)phenoxy]carbonyl]phenyl ester (OBDPE), have been carried out on the angular frequency range from 25.12 to 50265k rad/s at different temperatures. Thanks to dielectric measurements, real and imaginary dielectric constant, conductivity mechanism and dielectric relaxation mechanism of OBDPE were obtained.

Chiral and orientationally ordered fluid mesophases formed by oxadiazole bisaniline based achiral bent mesogens

ABSTRACTDevelopment of new liquid crystalline materials exhibiting interesting properties and phases continues to be an enabling enterprise in the forward march of their successful display and non-display applications. The design and synthesis of a homologous series of liquid crystalline bent-core compounds derived from the oxadiazole bisaniline moiety and the phase behavior of three members of the series that exhibit nematic, smectic C, and dark conglomerate phases is reported. The liquid crystalline phases exhibited by these mesogens are characterized using polarized optical microscopy, differential scanning calorimetry and x-ray scattering techniques. All three homologs prepared exhibit the nematic phase. Interestingly, the homolog with short hexyl terminal chains exhibits only the nematic phase that is stable over a very broad, nearly 100 K wide, temperature range. The compound with terminal octyl chains shows the chiral dark conglomerate phase below the nematic phase despite the bent molecules being achiral. The homolog with dodecyl alkyl chains is found to possess the smectic-C and two additional lamellar phases besides the nematic phase. These compounds enrich the library of achiral bent-core materials capable of exhibiting chiral and nematic phases.

Observation of polar order and thermochromic behaviour in a chiral bent-core system exhibiting exotic mesophases due to superstructural frustration.

A new approach accompanied by superstructural frustration is reported. By attaching a cholesterol moiety directly to the central bent-core system it displayed exotic BPIII, BPII/I, Ncyb*, TGBA, SmAPA, SmA and SmX phases as shown by X-ray scattering results. While higher homologues of the series exhibited spontaneous formation of polar order (Ps ∼ 61 nC cm-2) upon applied voltage, the lower homologues showed thermochromic behaviour which can also be trapped via temperature quenching.

From understanding structures in antiferro-ferri and ferroelelectric liquid crystals to an unusual electro-optic effect in a bent-core nematic; a celebration of innovative materials

ABSTRACTThe field of liquid crystals is truly multidisciplinary with numerous examples of virtuous circles of interaction between chemistry, physics, theory and engineering resulting in breakthroughs in both fundamental understanding and novel applications. This paper, written to mark John Goodby’s 65th birthday, offers a personal perspective of the synergy between chemistry and physics from a collaboration that has spanned three decades. The first part of the paper reviews some of the physics insights that resulted from chiral liquid crystals fundamental to understanding structures in ferroelectric, ferrielectric and antiferroelectric systems. The second part of the paper describes some of the remarkable consequences of the anomalous elasticity and flexoelectricity found in the nematic phases of bent-core materials. In particular, we present unusual bowing of disclination lines in the nematic phase of a bent-core material in the presence of a field. Finally, the paper summarises some future prospects relating for bent-core materials. The paper by no means captures the amazing breadth of contribution that John’s chemistry has made to the subject, but aims to exemplify how his generous collaborative approach coupled with innovative chemistry and physical insight has led to paradigm changes in our subject.

Observation of disordered mesomorphism in three-ring-based highly polar bent-core molecules: design, synthesis and characterisation

ABSTRACTResearch on low-temperature polar bent-core nematogens having lower molecular weight has gathered appreciable momentum by virtue of their significance in potential applications. However, the lack of availability and easy-to-perform synthesis processes appears to be the bottleneck towards their fabrication and thereby limiting their possible device applications. Hence, we have designed a new class of achiral symmetrical three-ring-based-bent shaped molecules incorporating an imine and ester linkage at the molecular bend with highly polar nitro/cyano terminal moiety exhibiting low-temperature nematic mesmorphism. The occurrence of disordered nematic mesomorphism has been confirmed by optical texture, differential scanning calorimetry scan and X-ray diffraction measurement. Dielectric spectroscopy and electro-optical investigation has also been carried out intending towards the potential applicability of the materials. Density functional theory analyses at the molecular level provide valuable information regarding the formation of the nematic mesophase and various parameters of the molecular spatial arrangement. Polarising optical microscopy study reveals the easy of alignment of these types of polar bent-core materials upon glass surface suitable for liquid-crystal-based sensing applications. Formation of mesophase with such a small bent molecule is rather difficult but we have successfully demonstrated the existence of disordered nematic mesomorphism at relatively low temperature.

Development of ferroelectricity in the smectic phases of 4-cyanoresorcinol derived achiral bent-core liquid crystals with long terminal alkyl chains

Bent-core molecules can form numerous polar and symmetry broken liquid crystalline phases with fascinating properties. Here we report the characteristics of a previously unknown polar synclinic smectic phase, $\mathrm{Sm}{C}_{\mathrm{S}}{P}_{\mathrm{X}}$, found in the phase sequence of an achiral bent-core material with a 4-cyanoresorcinol bisbenzoate core, terminated by long linear alkyl chains ($n=18$) on both ends. This phase exists over a narrow range of temperatures and is sandwiched in between the random polar synclinic smectic phase ($\mathrm{Sm}{C}_{\mathrm{S}}{P}_{\mathrm{R}}$) and polar synclinic ferroelectric ($\mathrm{Sm}{C}_{\mathrm{S}}{P}_{\mathrm{F}}$) phase with ${\mathbit{P}}_{S}\ensuremath{\sim}250\phantom{\rule{0.16em}{0ex}}\mathrm{nC}/\mathrm{c}{\mathrm{m}}^{2}$. In a planar-aligned cell it exhibits only chirality flipping on application of a conventional ac field but it also exhibits optical switching by rotation of the molecular directors on the tilt cone subjected to a modified sequence of bipolar pulses. This changeover is discussed in terms of the model given by Nakata et al. [Phys. Rev. Lett. 96, 067802 (2006)], involving a competition between the two forms of switching: the rotation around the long molecular axis and the switching through rotation of the molecular directors on the tilt cone. The model is modified to take account of the azimuthal pretilt and the molecular tilt angles. In addition to it, characteristics of $\mathrm{Sm}{C}_{\mathrm{S}}{P}_{\mathrm{R}}$ are also discussed.

Effect of linking groups on 2, 5-disubstituted thiophene with chalcone as the side arm containing bent-core materials

ABSTRACTNovel bent-core materials containing a central core of 2, 5-disubstituted thiophene with chalcone as the side arm were synthesized and characterized to determine the structure–property relationship. The structural difference between two materials is the linking group in the thiophene and chalcone side arm. Chalcone is linked with thiophene by ester group in material I, while ester group is replaced with imine group in material II. The change in linking group exhibited a drastic difference in their physicochemical and intramolecular behaviors. Material I exhibits a hexagonal columnar mesophase at below room temperature, whereas material II exhibits a crystalline phase. Both liquid crystalline and crystalline properties were examined from polarized optical microscopy (POM), differential scanning calorimetry (DSC), and powder X-ray diffraction (PXRD) analyses. The highlight of this work is material I revealed a hexagonal columnar phase in the temperature ranges 22–38°C and undergoes photocrosslinking in UV light; contrarily, material II exhibits neither LC phase nor photocrosslinking property.

Bent-core liquid crystals with a 2-substituted 3-hydroxybenzoic acid central core

ABSTRACTWe report the synthesis and study of the mesomorphic behaviour for a series of bent-core materials based on 2-substituted 3-hydroxybenzoic acid as a central unit. Properties of the studied compounds are tuned by lateral substitution (F, Cl, CH3, NO2 and CN) in the position 2 of 3-hydroxybenzoic acid and by the length of the terminal alkyl chain. All studied homologues exhibit at least one mesophase. Mesomorphic properties are established and compared with other 3-hyhroxybenzoic derivatives studied previously, with analogous orientation of ester linkages, laterally substituted at different position on the central core. The role of the substitution and the length of the terminal alkyl chain are discussed.

Elastic properties of bent-core nematic liquid crystals: the role of the bend angle

ABSTRACTThe nematic phase formed from bent-core liquid crystals has been the focus of intensive research for more than a decade. With the potential of biaxial nematic phase and other interesting features, such as high Kerr constants, large flexoelectric coefficients and anomalous elastic constants, these bent-core materials have been in the limelight of research. This paper presents a mini-review of the interesting elastic behaviour reported in various bent-core compounds. The review further focusses on two different types of bent-core compounds as exemplars: one derived from an oxadiazole and other a thiadiazole, highlighting the importance of bend angle in bent-core compounds. The universality of the unique behaviour of bend elastic constants via molecular field theory and atomistic modelling has also been summarised.

Second-harmonic generation and the influence of flexoelectricity in the nematic phases of bent-core oxadiazoles

ABSTRACTSecond-harmonic generation (SHG) in the nematic phase of bent-core oxadiazole-based liquid crystals (LCs) was studied and compared to that for the rod-like compound 4-cyano-4ʹ-n-octylbiphenyl (8CB). Weak, isotropically scattered second-harmonic (SH) light was observed for all materials, consistent with SHG by nematic director fluctuations. The SH intensity produced by the bent-core materials was found to be up to ~ 3.4 times that of 8CB. We discuss this result in terms of the dependence of SH intensity on temperature, elastic constants and flexoelectric coefficients. We have calculated the latter by using a molecular field approach with atomistic modelling, thus demonstrating how molecular parameters contribute to the flexoelectric coefficients and illustrating the potential of this method for predicting the flexoelectric behaviour of bent-core LCs. We show that the increased SH signal in the bent-core compounds is partly due to their nematic phases being at a much higher temperature, and also potentially due to them having greater flexoelectric coefficients, up to ~1.5 times those of 8CB. These estimates are consistent with reports of increased flexoelectric coefficients in bent-core compounds in comparison to rod-like compounds.

Modulated nematic structures induced by chirality and steric polarization.

What kind of one-dimensional modulated nematic structures (ODMNS) can form nonchiral and chiral bent-core and dimeric materials? Here, using the Landau-de Gennes theory of nematics, extended to account for molecular steric polarization, we study a possibility of formation of ODMNS, both in nonchiral and intrinsically chiral liquid crystalline materials. Besides nematic and cholesteric phases, we find four bulk ODMNS for nonchiral materials, two of which, to the best of our knowledge, have not been reported so far. These two structures are longitudinal (N_{LP}) and transverse (N_{TP}) periodic waves where the polarization field being periodic in one dimension stays parallel and perpendicular, respectively, to the wave vector. The other two phases are the twist-bend nematic phase (N_{TB}) and the splay-bend nematic phase (N_{SB}), but their fine structure appears more complex than that considered so far. The presence of molecular chirality converts nonchiral N_{TP} and N_{SB} into new N_{TB} phases. Surprisingly, the nonchiral N_{LP} phase can stay stable even in the presence of intrinsic chirality.

Monolayer Filaments versus Multilayer Stacking of Bent-Core Molecules.

Bent-core materials exhibiting lamellar crystals (B4 phase), when dissolved in organic solvents, formed gels with helical ribbons made of molecular monolayers and bilayers, whereas strongly deformed stacks of 5-6 layers were found in the bulk samples. The width and pitch of the helical filaments were governed by molecular length; they both increased with terminal-chain elongation. It was also found that bulk samples were optically active, in contrast to the corresponding gels, which lacked optical activity. The optical activity of samples originated from the internal structure of the crystal layers rather than from the helicity of the filaments. A theoretical model predicts a strong increase in optical activity as the number of layers in the stack increases and its saturation for few layers, thus explaining the smaller optical activity for gels than for bulk samples. A strong increase and redshift in fluorescence was detected in gels as compared to the sol state.

Nanoscale structures of polarisation-modulated bent-core materials in thin films

We present small angle X-ray and cryogenic transmission electron microscopy (cryo-TEM) studies of three nitro-substituted (n-OPIMB-NO2, n = 7, 9 and16) bent-core liquid crystals (LCs) that form peculiar optical patterns known as B7 textures. Small angle X-ray scattering studies show two periodicities between a ~ 3.4–4.7 nm and bX ~ 9–16 nm. Cryo-TEM images of about 100 nm thick films do not show the a-periodicity, but only periodicities bT that are about 1 nm smaller than bX measured in bulk by X-ray. Additionally, an intensity modulation with a period c ~ 100–200 nm is observed. These observations can be explained by a B1-type structure, where there are half-layer step discontinuities at the boundaries of the splay domains, and where the molecules are everywhere normal to the substrate.

Three-Ring-Based Room-Temperature Bent-Core Nematic Compounds: Synthesis and Characterization.

We report the synthesis and characterization of a new class of achiral three-ring bent-core compounds with an amide and ester linkage at the molecular bend, which are shown to exhibit nematic/phases in wide temperature ranges around room temperature (RT) and undulated SmC phases below RT. In contrast to previous studies, the compounds reported in this Communication show a true RT nematic phase with fluid physical appearance. They show strong photoluminescence in the mesophase and are found to display a one-dimensional array of intermolecular hydrogen bonding. Furthermore, the nematic phases exhibited by these compounds show a good homeotropic alignment that can be exploited in applications such as optics and sensing. Considering the scarcity of bent-core materials exhibiting an RT nematic mesophase, this new class of materials is promising.

Field alignment of bent-core smectic liquid crystals for analog optical phase modulation

A general method for aligning bent-core smectic liquid crystal materials is described. Alternating electric fields between interdigitated electrodes patterned on one cell surface create torques on the liquid crystal that result in uniform “bookshelf” orientation of the smectic layers. The aligned cell can then be driven in the conventional way by applying an electric field between all of the stripe electrodes connected together and a monolithic electrode on the other cell surface. Fast, analog, optical phase-only modulation is demonstrated in a device containing a polar, bent-core SmAPF material aligned using this technique.

Viscoelastic behavior of a binary system of strongly polar bent-core and rodlike nematic liquid crystals.

We have investigated the permittivity and viscoelastic behavior of a binary system comprising bent-core and calamitic compounds, both of which are polar, the calamitic being more strongly so, and exhibiting only the nematic mesophase. The permittivity data in the nematic as well as the isotropic phase indicate strong polar interactions between the molecules, even for mixtures with a significant content of the bent-core compound. The thermal dependence of both the splay and bend elastic constants exhibit features different from the literature. The splay constant displays a large increase with increasing concentration of bent-core material, before undergoing a precipitous drop for small calamitic content materials. Upon lowering the temperature, certain mixtures exhibit a convex-shaped feature for the bend elastic constant; that is, the value of the elastic constant is maximum at a specific temperature in the nematic phase, diminishing when the temperature is either increased or decreased. Surprisingly, the pure compounds, especially the bent-core one, show only a monotonically increasing trend for the bend elastic constant. We present two arguments to explain these features: one of these is based on coupling between the molecular shape and director distortion presented in the literature. Then we put forth a new concept of frustration in the packing between the two types of molecules and the polar interactions as an alternative.

ChemInform Abstract: Liquid Crystals of the Twenty‐First Century ‐ Nematic Phase of Bent‐Core Molecules

AbstractReview: 171 refs.

The Nematic Phases of Bent‐Core Liquid Crystals

Over the last ten years, the nematic phases of liquid crystals formed from bent-core structures have provoked considerable research because of their remarkable properties. This Minireview summarises some recent measurements of the physical properties of these systems, as well as describing some new data. We concentrate on oxadiazole-based materials as exemplars of this class of nematogens, but also describe some other bent-core systems. The influence of molecular structure on the stability of the nematic phase is described, together with progress in reducing the nematic transition temperatures by modifications to the molecular structure. The physical properties of bent-core nematic materials have proven difficult to study, but patterns are emerging regarding their optical and dielectric properties. Recent breakthroughs in understanding the elastic and flexoelectric behaviour are summarised. Finally, some exemplars of unusual electric field behaviour are described.

Cryo-TEM studies of two smectic phases of an asymmetric bent-core material

Cryo-TEM studies on two smectic phases of an asymmetric bent-core liquid crystal material are presented and compared to prior X-ray results obtained in bulk samples. While the bulk samples have layer-modulated structures, those modulations are not observable in the 100-nm-thick TEM samples, indicating surface-induced suppression of the layer modulations. The observed layer spacing is in agreement with the X-ray results in the lower temperature smectic phase, but distinctly larger in the higher temperature phase. This indicates surface-induced suppression of the director tilt. Cryo-TEM textures resolve the profiles of individual smectic layers at the scales down to few nanometres and reveal the presence of edge and screw dislocations, twist grain boundaries, small-angle and large-angle tilt grain boundaries.

Liquid crystals of the twenty-first century – nematic phase of bent-core molecules

Bent-core (BC) materials that form nematic liquid crystals (BC nematics (BCNs)) are known only since 2000, but since then they have been intensively studied. In this review we give a comprehensive summary of the main research directions and results. After discussing representative examples of molecules making BCNs, we review theoretical predictions and experimental findings about macroscopic symmetries, such as chirality of achiral and chiral molecules, tetrahedratic symmetry and phase biaxiality versus uniaxiality. Then we describe the properties of smectic nano clusters often observed in BCNs, and discuss rheological properties that reveal unusually large viscosities and small twist and bend elastic constants. Finally, we focus on the electric properties of BCNs, such as dielectric and ferroelectric properties, electroconvection (EC) and electromechanical effects.