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Computational calculations predict the dichroic ratios of a range of anthraquinone and azo dyes in a nematic liquid crystal host, as observed experimentally from polarized spectra of aligned guest–host samples.

The recently discovered ferroelectric nematic liquids incorporate to the functional combination of fluidity, processability and anisotropic optical properties of nematic liquids, an astonishing range of physical properties derived from the phase polarity. Among them, the remarkably large values of second order optical susceptibility encourage to exploit these new materials for non-linear photonic applications. Here we show that photopatterning of the alignment layer can be used to structure polarization patterns. To do so, we take advantage of the flexoelectric effect and design splay structures that geometrically define the polarization direction. We demonstrate the creation of periodic polarization structures and the possibility of guiding polarization by embedding splay structures in uniform backgrounds. The demonstrated capabilities of polarization patterning, open a promising new route for the design of ferroelectric nematic based photonic structures and their exploitation. Ferroelectric Nematic Liquid Crystals (FNLCs) have potential in applications due to their unique combination of fluidity, spontaneous polarization, large dielectric permittivity, and second-order non-linear optical properties. Sebastian et al. show the patterning of electric polarization in FNLCs by photoalignment which exploit flexoelectric coupling between polarization and splay director deformations.

The recent discovery of the ferroelectric splay nematic phase has opened the door to experimental investigation of one of the most searched liquid crystal phases in decades, with high expectations for future applications. However, at this moment, there are more questions than answers. In this work, we examine the formation and structure of large polar nematic domains of the ferroelectric splay nematic material RM734 in planar liquid crystals cells with different aligning agents and specifications. We observe that confining surfaces have a strong influence over the formation of different types of domains, resulting in various twisted structures of the nematic director. For those cells predominantly showing mm-scale domains, we investigate the optical and second harmonic generation switching behaviour under applications of electric fields with a special focus on in-plane fields perpendicular to the confinement media rubbing direction. In order to characterize the underlying structure, the polar optical switching behaviour is reproduced using a simplified model together with Berreman calculations., Comment: 16 pages Main Manuscript, 15 pages Supporting Information, 28 Figures

The recent discovery of the splay nematic phase, a new nematic polymorph that has been found to be both polar and ferroelectric, is the lead paragraph in an entirely new chapter in the history of l...

The ferroelectric nematic (NF) phase, characterised by the combination of orientational and polar order, offers unique properties that are challenging to replicate in other systems. Understanding the molecular structure requirements for generating the NF phase is crucial for the design of new materials with enhanced properties. This study investigates UUQU-4-N, a room-temperature NF material, using fully atomistic molecular dynamics simulations. UUQU-4-N does not spontaneously form an apolar nematic phase in silico, but exhibits a stable polar nematic configuration akin to the NF phase. The polar order remains significant and near saturation throughout the simulations. The study also examines the cylindrical pair correlation functions, providing insights into the preferred pairing modes and intermolecular interactions which we can then attribute to specific molecular features. We then simulate structural variants of UUQU-4-N, highlighting the potential for developing further examples of near-room-temperature ferroelectric nematic materials via the manipulation of the fluorination pattern, variations in terminal chain length, and replacement of the difluoromethyleneoxy linker.

In this work, a two-component acrylate liquid crystal elastomer, with varying composition and templating phase, is synthesized in the laboratory and investigated in parallel using atomistic molecular dynamics simulations. The anisotropic nature of both the mono- and bifunctional acrylates used in this study enables a large tunability in the compositional range while still retaining liquid crystalline properties in the final elastomer. The use of simulations allows important evaluation and comparison of physical properties such as glass transition temperature, nematic to isotropic phase transition temperature, and order parameter. The dependence of physical properties (glass transition, nematic to isotropic transition, order parameter, coefficient of thermal expansion, and mechanical properties) is established as a function of chemical composition, showing a high degree of tunability. Interestingly, the templating phase (nematic or isotropic) is also shown to impact the subsequent elastomer properties, with excellent agreement shown here between experiments and simulations. The in silico approach to polymerization, coupled with excellent comparison with the experimental system, represents a new methodology for the targeted design of liquid crystal elastomers with specific physical properties.

In ancient Roman religion and myth, Janus is the god of beginnings, gates, transitions, time, duality, doorways, passages, frames, and endings. He is usually depicted as having two faces looking in opposite directions, one towards the past and the other towards the future. This article is dedicated to Professor BK Sadashiva for his contributions to the science of liquid crystals, and new beginnings in the design and creation of mesomorphic materials. In the studies of metallomesogens based on copper(II) complexes of β-diketones, Ohta and his colleagues reported the first-established discotic-lamellar phase, in which the board-like complexes are able to form lamellar packing arrangements, and at the same time stacking into columns. Casagrande et al. later prepared synthetically modified beads with one hemisphere being hydrophobic and the other hydrophilic. These particles were considered to be amphiphilic solids, and called Janus Beads. Synthetic Janus Mesogens with supermolecular architectures having one chiral nematic hemisphere and the other with smectic tendencies were made in 2003. These complexes, particles, and supermolecules, were termed Janus to describe the structure of the material. In this article we use Janus liquid crystals to describe a material that combines two different packing motifs in a single uniform phase structure.

Nematic liquid crystals have been known for more than a century, but it was not until the 60s-70s that, with the development of room temperature nematics, they became widely used in applications. Polar nematic phases have been long-time predicted, but have only been experimentally realized recently. Synthesis of materials with nematic polar ordering at room temperature is certainly challenging and requires a deep understanding of its formation mechanisms, presently lacking. Here, we compare two materials of similar chemical structure and demonstrate that just a subtle change in the molecular structure enables denser packing of the molecules when they exhibit polar order, which shows that reduction of excluded volume is in the origin of the polar nematic phase. Additionally, we propose that molecular dynamics simulations are potent tools for molecular design in order to predict, identify and design materials showing the polar nematic phase and its precursor nematic phases., 33 pages, 21 of main manuscript and 12 of Supporting Information, 7 main figures

The NTB phase phases possess a local helical structure with a pitch length of a few nanometers and is typically exhibited by materials consisting of two rigid mesogenic units linked by a flexible oligomethylene spacer of odd parity, giving a bent shape. We report the synthesis and characterisation of two novel dimeric liquid crystals, and perform a computational study on 10 cyanobiphenyl dimers with varying linking groups, generating a large library of conformers for each compound; this allows us to present molecular bend angles as probability weighted averages of many conformers, rather than use a single conformer. We validate conformer libraries by comparison of interproton distances with those obtained from solution‐based 1D 1H NOESY NMR, finding good agreement between experiment and computational work. Conversely, we find that using any single conformer fails to reproduce experimental interproton distances. We find the use of a single conformer significantly overestimates the molecular bend angle while also ignoring flexibility; in addition, we show that the average bend angle and flexibility are both linked to the relative stability of the NTB phase., Bend it like Mandle! Conformational analysis of liquid crystalline dimers, validated by comparison of computed and experimental 1H NOESY NMR data is used to analyse average molecular shape, which is demonstrated to underpin the formation of the liquid crystalline heliconical nematic NTB phase.

Twist-bend (TB) phases possess a local helical structure with a pitch length of a few nanometers. The TB phase was first observed in low molecular weight dimers, and as such these have been the focus of efforts to understand the properties and structure of these new phases of matter. Recently several oligomeric and polymeric materials have been reported, but there is little information on the properties and structure of the TB phase in these materials. Herein we compare the order parameters, orientational distribution functions (ODF) and heliconical tilt angles of the TB phase exhibited by a liquid-crystalline dimer (CB7CB) to a tetramer (O47) and hexamer (O67) by SAXS/WAXS. Following the N-TB phase transition we find that all order parameters decrease, and while 〈P2〉 remains positive 〈P4〉 becomes negative. For all three materials the order parameter 〈P6〉 is near zero in both phases. The ODF is sugarloaf-like in the nematic phase and volcano-like in the TB phase, allowing us to estimate the heliconical tilt angle of each material and its thermal evolution. Surprisingly, the heliconical tilt angle appears to be largely independent of the material studied despite the differing number of mesogenic units.

The term liquid crystal elastomer (LCE) describes a class of materials that combine the elastic entropy behaviour associated with conventional elastomers with the stimuli responsive properties of anisotropic liquid crystals. LCEs consequently exhibit attributes of both elastomers and liquid crystals, but additionally have unique properties not found in either. Recent developments in LCE synthesis, as well as the understanding of the behaviour of liquid crystal elastomers—namely their mechanical, optical and responsive properties—is of significant relevance to biology and biomedicine. LCEs are abundant in nature, highlighting the potential use of LCEs in biomimetics. Their exceptional tensile properties and biocompatibility have led to research exploring their applications in artificial tissue, biological sensors and cell scaffolds by exploiting their actuation and shock absorption properties. There has also been significant recent interest in using LCEs as a model for morphogenesis. This review provides an overview of some aspects of LCEs which are of relevance in different branches of biology and biomedicine, as well as discussing how recent LCE advances could impact future applications.

Polar-terminated 3,5-diarylisoxazole liquid crystals (ILCs) were synthetized and characterized. ILCs are composed by rigid core 3,5-diarylisoxazol, alkyl chain and polar-terminated flexible spacer. Hydroxyl-, ketal- and 1,2-diol-terminated ILCs rendered smectic C and A mesophase, while bromine-terminated ILCs showed smectic A and B mesophase, for monosubstituted and linear ILCs. For branched alkyl chain monotropic SmA was detected and for disubstituted ILCs no mesophase was detected. Out-of-layer fluctuations (OLFs) are discussed based on X-ray diffraction date and textures. The OLFs are dependent on the bromine atom hardness, hydrogen bonding through collective actions and conformational effects at the interface between layers. Smectic translational order parameter (TOP) Σ was also obtained for orientated bromine- and hydroxyl-terminated ILCs and related it with OLFs. For 1,2-diol-terminated ILCs two SmC sublayers were founded, probably related to the intramolecular hydrogen bond favoring the 5-membered and 6-membered formation.

The nematic twist-bend (NTB ) liquid crystal phase possesses a local helical structure with a pitch length of a few nanometres and is the first example of spontaneous symmetry breaking in a fluid system. All known examples of the NTB phase occur in materials whose constituent mesogenic units are aromatic hydrocarbons. It is not clear if this is due to synthetic convenience or a bona fide structural requirement for a material to exhibit this phase of matter. In this work we demonstrate that materials consisting largely of saturated hydrocarbons can also give rise to this mesophase.

Nematic liquid crystals lack positional order of their constituent molecules, which share an average orientational order only. Modulated nematic liquid crystal phases also lack positional order, but possess a periodic variation in this direction of average orientation. In the recently discovered splay nematic (NS) phase the average orientational order is augmented with a periodic splay deformation of orientation perpendicular to the director. In this communication we report the first example of a splay nematic phase which is chemically induced by mixing two materials, neither of which exhibit the NS phase. The splay-nematic phase is identified based on its optical textures, X-ray scattering patterns, and small enthalpy of the associated phase transition. We measure the splay periodicity optically, finding it to be ∼9 μm. This unexpected generation of the splay-nematic phase through binary mixtures offers a new route to materials which exhibit this phase which complements ongoing studies into structure–property relationships and could accelerate the development of technologies utilising this remarkable polar nematic variant.

Arguably the most active area in liquid crystal research presently, the twist-bend modulated nematic phase (TB) exhibits a nanoscale helical structure and therefore exhibits bulk chirality despite being formed of typically achiral materials. After a short introduction we address the structure-property relationship that exists for this unique mesophase before introducing recent advances in strategies employed to prepare oligomeric materials that exhibit this state of matter. These methods afford fine control over the molecular substructure and potentially over the nanostructure of the exhibited mesophases.

The nematic twist-bend (NTB) liquid crystal phase possesses a local helical structure with a pitch length of a few nanometres and is the first example of spontaneous symmetry breaking in a fluid system. All known examples of the N­TB­ phase occur in materials whose constituent mesogenic units are aromatic hydrocarbons. It is not clear if this is due to synthetic convenience or a bona fide structural requirement for a material to exhibit this phase of matter. In this work we demonstrate that materials consisting largely of saturated hydrocarbons could also give rise to this mesophase. Furthermore, replacement of 1,4-disubstituted benzene with trans 1,4-cyclohexane or even 1,4-cubane does not especially alter the transition temperatures of the resulting material nor does it appear to impact upon the heliconical tilt angle, suggesting the local structure of the phase is unperturbed. Calculating the probability distribution of bend angles reveals that the choice of isosteric group has little impact on the overall molecular shape, demonstrating the shape-driven nature of the NTB phase.

The nematic liquid-crystalline phase exhibits average orientational order, with no positional organisation. So-called modulated nematic phases exhibit this same orientational order with an additional spatially periodic modulation of the nematic director, the most common of which is the twist-bend nematic phase. We report a pentaerythritol derived tetrapode which exhibits a nematic-like mesophase at ambient temperature, and we denote this new mesophase 'NX ' to indicate a nematic phase of unknown structure. X-ray scattering experiments refute the possibility of positional order, yet optical textures are consistent with a periodic structure. We suggest that the mesophase exhibited by this material is a new type of nematic-like mesophase with some form of modulated structure. We find the NX phase to exhibit an electrooptic response consistent with a nematic-like phase.

In this study, polymer dispersed liquid crystal composite films are obtained via a one-step fabrication technique based on photo-initiated polymerization-induced phase separation in a thiol-vinyl ether reaction. The effects of the compositions of two vinyl monomers, curing light intensity, curing light time, liquid crystal content and thiol content on the electro-optic properties of the polymer dispersed liquid crystal films were systematically investigated. It was demonstrated that a composite film with a low driving voltage (33.7 V), high contrast ratio (228.1) and short response time (

The twist-bend nematic phase (NTB ) has been described as the structural link between the untilted uniaxial nematic phase (N) and the helical chiral nematic phase (N*). The NTB phase exhibits phenomena of fundamental importance to science, that is, 1) the spontaneous formation of a helical pitch on the nanometer scale in a fluid and 2) the spontaneous breaking of mirror symmetry, leading to the emergence of chiral domains in an achiral system. In this Communication, we present a study on T49 [bis(4-(9-(4-((4-cyanobenzoyl)oxy)phenyl)nonyl)phenyl) 4,4'-(nonane-1,9-diyl)dibenzoate], a liquid-crystalline oligomer exhibiting the twist-bend nematic phase, which has a molecular length that is of comparable dimensions to the sub-10 nm pitch determined for CB9CB, and provide new insights into the differentiation between the nano- and macro-science for self-assembling supermolecular systems.

In this article we report on the characterization and properties of several unsymmetrical phenyl-benzoate bimesogens that exhibit the soft-matter, twist-bend nematic (NTB) phase. We use this study as a basis to examine the phase behaviour of associated novel trimeric and tetrameric materials, in order to investigate the potential for oligomeric materials to form the NTB phase. Based on our results we hypothesise that higher oligomers and even polymers are highly likely to exhibit the NTB phase, provided they retain a gross bent structure between consecutive mesogenic units. Thus we show at the level of nanoscale organization, dimers can template with respect to one another to form mesophases that are also found in macromolecular systems.

A number of new states of matter have been reported in recent years for liquid crystal dimers, most notably the twist-bend nematic phase which exhibits spontaneous breaking of symmetry through the emergence of chiral structures in an achiral fluid. In this communication we report on an unsymmetrical liquid crystal dimer that exhibits a transition from the spontaneously chiral twist-bend nematic phase into a novel smectic liquid crystal phase.

Two series of Schiff base (SB) liquid crystals (LC) containing the 5-membered rings isoxazoline or isoxazole were synthesized and characterized; 27 isoxazoline and 20 isoxazole compounds were obtained. Nematic, smectic A, and smectic C mesophases were found and characterized by Polarized optical microscopy (POM), Differential scanning calorimetry (DSC), and X-ray diffraction. The scientific problem addressed was how the isoxazoline and isoxazole rings affect the mesophase structure and stability. Molecular packing and anisotropic interactions based on enthalpy and entropy properties were used to explain the thermal and structural behaviour observed for both series. The proposed mechanism was assisted by Density functional theory (DFT) calculations, providing new insights into the molecular organization of this kind of system.

The mesogenic dimer displaying nematic and NTB phases was investigated by resonant X-ray scattering at both C and S absorption K-edges and supported by single X-ray crystallography. In the crystal resonant studies revealed the forbidden reflection in non-resonant diffraction similar to that found in the NTB phase. The lack of a second harmonic in both C and S resonant X-ray scattering supports the double helical structure of the twist-bend nematic phase.

Nanoscale phase separation and self-organisation in liquid crystals leads to the formation of remarkable hierarchical structures. There are several examples of heliconical nanofilament structures including in the nematic twist-bend (NTB) phase, the B4 phase and liquid crystal gels formed from the B4 phase. Both the formation of the polymer-like structures that permeate the soft-solids and their hierarchical structures are fascinating, not least because of the analogies that can be drawn with naturally-occurring structures. Here, we report a remarkably simple binary system formed from a non-symmetric BC molecule and the rod-like liquid crystal, 5CB. The pure bent-core system exhibits both nematic and dark conglomerate liquid crystal phases. At very low concentrations of the BC material (5-10%) this binary system spontaneously self-assembles into a soft solid formed from nanoscale filaments that are aligned by their nematic environment. Macroscopically, the soft solid shows behaviour that can be associated with both polymers and gels. Interestingly, the sub-micron scale structure of the filaments appears remarkably similar to some organised fibrous structures in nature (e.g. chitin, cellulose, insect cuticle, plant cell walls) something we attribute to self-assembly and self-organisation in an aligned liquid crystalline environment. The nanoscale structure of the filaments shows no features that can be associated with heliconical ordering down to length scales of tens of nanometers. However, the X-ray data suggest that a metastable rectangular columnar phase which is highly ordered in one dimension initially forms, changing to a hexagonal lattice on a timescale of tens of minutes. © The Royal Society of Chemistry.

From the observation of a previously undiscovered nematic-like mesophase (NX) by Archbold et al., we report on several new binary liquid-crystalline mixtures between the high helical twisting power dopant RM1041 and a selection of dimers with varying average bend angles and conformational landscapes. We also report on mixtures between RM1041 and oligomeric LC materials. We find that dimers and oligomers exhibit not only chiral nematic and twist-bend modulated phases, but also the same NX phase reported by Archbold, indicating that this state of matter (the structure of which is yet to be definitively characterised) is exhibited by a wide range of materials. Mixtures of the dimer CB9CB with a selection of different chiral dopants suggest that it is the helical twisting power of the chiral additive that is responsible incidence of the NX phase.

Liquid crystalline phases with a spontaneous twist-bend modulation are most commonly observed for dimers and bimesogens with nonamethylene spacers. In order to redress this balance we devised a simple chemical intermediate that can be used to prepare unsymmetrical bimesogens; as a proof of concept we prepared and studied eleven novel materials with all found to exhibit the twist-bend phase and exhibit a linear relationship between TN-I and TTB-N. A computational study of the conformational landscape reveals the octamethyleneoxy spacer to have a broader distribution of bend-angles than the nonamethylene equivalent, leading to reductions in the thermal stability of the TB phase. This result indicates that a tight distribution of bend-angles should stabilise the TB phase and lead to direct TB-Iso phase transitions, and conversely a broader distribution should destabilise the TB phase which may allow new states of matter that are occluded by the incidence of this phase to be revealed.

In the current fascination with liquid crystalline dimers, bimesogens and oligomers the role of the central spacer in these systems has perhaps been somewhat neglected. In compound 1, a phenyl 4-cyanobenzoate bimesogen, the central spacer incorporates a methyl group at the 2-position and is therefore chiral. The helical twisting power of 1, measured in both 5CB and E7, was found to be 0.36 and 0.35 μm

Herein we report a comprehensive study on novel carbonyl- and ethenyl-linked symmetric dimers that combine synthesis, mesomorphic properties and molecular modelling. The study has been focused on the impact of geometry imposed by the linkage group on the incidence of the twist-bend nematic (NTB) phase. Comparison of the mesomorphic properties of these two series complemented with computational studies of conformational space around the linkage group points molecular curvature and intramolecular torsion plays important role in the appearance of the NTB phase and can be regarded as the basic structural requirements for design of new twist-bend nematogen materials.

In this letter we describe the application of metallaphotoredox cross-electrophile couplings to the synthesis of liquid crystals using dual nickel and iridium catalysis. Given the proliferation of aryl and alkyl bromides in liquid crystal research we consider that the silyl-radical mediated cross-coupling of alkyl bromide with an aryl bromide (to afford a direct alkyl–aryl bond) will become an extremely powerful tool in the synthesis of liquid crystalline materials, and we use this to synthesise several well-known materials (PCH32, 5CB, CB7CB and CB15) in a single synthetic step from inexpensive and commercially available building blocks. The metallaphotoredox decarboxylative sp3–sp2 cross-coupling of an aryl bromide with an alkyl carboxylic acid provides a complimentary method to form alkyl–aryl bonds, and we use this to successfully prepare trans PCH5 in a single synthetic step from commercially available building blocks. We also prepare novel methylene-linked materials in a single synthetic step, one of which exhibit the topical TB phase.

The nematic twist-bend phase (NTB) was, until recently, only observed for polar mesogenic dimers, trimers or bent-core compounds. In this article, we report a comprehensive study on novel apolar materials that also exhibit NTB phases. The NTB phase was observed for materials containing phenyl, cyclohexyl or bicyclooctyl rings in their rigid-core units. However, for materials with long (>C7) terminal chains or mesogenic core units comprising three ring units, the NTB phase was not observed and instead the materials exhibited smectic phases. One compound was found to exhibit a transition from the NTB phase to an anticlinic smectic C phase; this is the first example of this polymorphism. Incorporation of lateral substitution with respect to the central core unit led to reductions in transition temperatures; however, the NTB phase was still found to occur. Conversely, utilising branched terminal groups rendered the materials non-mesogenic. Overall, it appears that it is the gross molecular topology that drives the incidence of the NTB phase rather than simple dipolar considerations. Furthermore, dimers lacking any polar groups, which were prepared to test this hypothesis, were found to be non mesogenic, indicating that at the extremes of polarity these effects can dominate over topology.

The relationship between molecular association and re-entrant phase behavior in polar calamitic liquid crystals has been explored in two families of materials: the 4'-alkoxy-4-cyanobiphenyls (6OCB and 8OCB) and the 4'-alkoxy-4-nitrobiphenyls. Although re-entrant nematic phase behavior has previously been observed in the phase diagram of 6OCB/8OCB, this is not observed in mixtures of the analogous nitro materials. As there is no stabilization of the smectic A phase in mixture studies, it was conjectured that the degree of association for the nitro systems is greater than that for the cyano analogues. This hypothesis was tested by using measured dielectric anisotropies and computed molecular properties to obtain a value of the Kirkwood factor, g, which describes the degree of association of dipoles in a liquid. These computed values of g confirm that the degree of association for nitro materials is greater than that for cyano and offer a useful method for quantifying molecular association in systems exhibiting a re-entrant polymorphism.

Polarized Raman Spectroscopy (PRS) is used to quantify the orientational order in the conventional (N) and twist-bend (NTB) nematic phases of a homologous series of liquid crystalline dimers. The dimers investigated have 7, 8, 9 and 11 methylene groups connecting two cyanobiphenyl mesogens and data for 4-pentyl-4′-cyanobiphenyl (5CB) and 4-octyl-4′-cyanobiphenyl (8CB) are included for comparison. Simulated and measured Raman spectra for the materials are compared. PRS is used to determine both 〈P2〉 and 〈P4〉 order parameters across the nematic temperature range and immediately below the NTB–N phase transition using a model that takes into account the molecular bend of the odd dimers, which is described in detail. In the nematic phase, the odd dimers are found to exhibit rather low order parameters with 〈P2〉 taking values between 0.3 and 0.5 and 〈P4〉 about 0.25. In contrast, the even dimer shows extremely high values of the order parameters with 〈P2〉 taking values between 0.7 and 0.8 and 〈P4〉 between 0.4 and 0.45. For the odd dimers, the values of 〈P2〉 in the NTB phase are similar to those of the N phase, whereas 〈P4〉 jumps by approximately 5–10% and then decreases with temperature. On comparing the experimental data with the theoretical predictions, we find reasonable qualitative agreement for all materials with molecular field theory. The odd dimers, however, show higher 〈P4〉 values than obtained from theoretical models, a factor attributed to the neglect of molecular flexibility and biaxiality in the PRS analysis.

A large selection of photochromic dihydroazulene (DHA) molecules incorporating various substituents at position 2 of the DHA core was prepared and investigated for their ability to form liquid crystalline phases. Incorporation of an octyloxy-substituted biphenyl substituent resulted in nematic phase behavior and it was possible to convert one such compound partly into its vinylheptafulvene (VHF) isomer upon irradiation with light when in the liquid crystalline phase. This conversion resulted in an increase in the molecular alignment of the phase. In time, the meta-stable VHF returns to the DHA where the alignment is maintained. The systematic structural variation has revealed that a biaryl spacer between the DHA and the alkyl chain is needed for liquid crystallinity and that the one aromatic ring in the spacer cannot be substituted by a triazole. This work presents an important step towards employing the dihydroazulene-vinylheptafulvene photo/thermoswitch in photoactive liquid crystalline materials.

A number of materials derived from 4-undecyloxy-4′-cyanobiphenyl but with varying terminal groups were prepared in order to better understand how such a group influences the type, and local structure of mesophases formed. Whereas electron poor terminal groups (fluoroaromatics and halogen atoms) were found to destabilise the smectic A phase through unfavourable electrostatic interactions, bulky silane, siloxane and hydrocarbon groups can be incorporated into the structure of the phase with only minor reductions in clearing point. An increase in the layer spacing of the smectic Ad phase in materials with bulky groups suggests that microphase segregation is not the driving force, but rather exists as a consequence of steric crowding at the smectic layer interface. Electrooptic studies reveal that ‘carbosilane’ end groups, such as tetramethyldisilapropane, are significantly more electrochemical stable than their siloxane counterparts whilst retaining their desirable thermal properties.

Ferroelectric liquid crystals are of interest in display devices because of their bistable operation and fast response times. However, they have not reached their potential for a number of reasons, low tilt angle and high birefringence being two of them. Although low birefringence can be achieved by incorporation of carbocyclic rings into the molecular structures of the materials this often lowers the occurrence of tilted phases, and additionally a high tilt angle is often very difficult to engineer. In this article we attempt to resolve these issues and demonstrate that through the incorporation a bulky terminal group attached to an external aliphatic chain in the molecular design, it is possible via size exclusion to achieve high tilt angles. We explore the conformational landscape of these materials with a combination of molecular modelling and NOE enhancements in 1H NMR.

A novel, highly polar rod-like liquid crystal was found to exhibit two distinct nematic mesophases (N and N

Photoswitches and dyes in the liquid-crystalline nematic phase have the potential for use in a wide range of applications. A large order parameter is desirable to maximize the change in properties induced by an external stimulus. A set of photochromic and nonphotochromic dyes were investigated for these applications. It was found that a bent-shaped 7-substituted dihydroazulene (DHA) photoswitch exhibited liquid-crystalline properties. Further investigation demonstrated that this material actually followed two distinct reaction pathways on heating, to a deactivated form by a 1,5-sigmatropic shift and to a linear 6-substituted DHA. In addition, elimination of hydrogen cyanide from the photoactive DHA gave both bent and linear azulene dyes. In a nematic host that has no absorbance around 350 nm, it was found that only the linear DHA derivative has nematic properties; however, both 6- and 7-substituted DHAs were found to have large order parameters. In the nematic host, ring opening of either DHA to the corresponding vinylheptafulvene resulted in a decrease in dichroic order parameter and an unusually fast back-reaction to a mixture of both DHAs. Likewise, only the linear azulene derivative showed mesomorphic properties. In the same nematic host, large order parameters were also observed for these dyes.

The twist–bend nematic (NTB) phase is a recently discovered liquid‐crystalline phase that exhibits macroscopic chirality even when formed from achiral materials, and as such presents a unique testbed for studies concerning the spontaneous breaking of mirror symmetry in soft matter. It is primarily exhibited by materials for which the molecular structure is composed of two rigid aromatic units (such as biphenyl connected by a flexible spacer). The local structure of the NTB phase is nematic‐like—with molecules having an average orientational order but no positional order—with a nanoscale helix in which the pitch (i.e., the repeat distance of the helix) is of the order of several nanometres. A helix is chiral, and so the bulk NTB phase—in the absence of a biasing chiral environment—spontaneously separates into macroscopic domains of opposite handedness. After discussing the structure of this mesophase and its elucidation, this concept article presents the molecular factors that determine its incidence. The apparent dependency primarily on molecular shape and bend angle rather than particular functional group combinations manifests in this mesophase being exhibited on length scales far beyond those of simple liquid‐crystalline dimers, not only in oligomers and polymers, but also in aqueous suspensions of micron sized helical particles.

In this work, we present the first part of a study into the relationship between molecular structure and the occurrence of the ‘twist-bend nematic phase’ (NTB). Given the large amount of chemical s...

In this article, we report on the liquid-crystalline properties of two series of halogen-terminated cyanobiphenyl-based materials. Unlike other rod-shaped, halogen-terminated materials reported, these materials do not exhibit the smectic A phase and instead only exhibit nematic liquid-crystal mesomorphism. Comparisons between these materials and analogous unsubstituted materials were made, and the relationships between their molecular structures and phase behaviour are discussed with the aid of molecular modelling at the B3LYP/6-31G* level of density functional theory.

A detailed microscopy study of the mesophases of 1,11-di-(1′′-cyanobiphenyl-4-yl)undecane (CB11CB) was undertaken, with an emphasis on attempting to relate the recent helical “twist-bend” model of the NTB phase to the observed optical textures. Our ability to draw a freestanding film indicates that the phase is unlikely to be nematic and possesses long range periodicity. No electrooptic response could be detected in the NTB phase, with or without addition of a chiral dopant although dielectric breakdown and space charge were observed at high voltage leading to field dependent pulsing of the sample. No optical rotation associated with a macroscopic helical structure could be discerned in the NTB phase. However, this observation could be taken to be in keeping with the extremely short pitch of a proposed “twist-bend” model.