Dyes for guest-host liquid crystal applications: a general approach to the rapid computational assessment of useful molecular designs.

A set of experimental dichroic order parameters ranging from +0.66 to -0.22 was obtained by recording polarized UV-visible absorption spectra from aligned samples of fifteen different guest anthraquinone and azo dyes in the nematic host 4-cyano-4'-pentylbiphenyl (5CB).

Experimental and Computational Study of a Liquid Crystalline Dimesogen Exhibiting Nematic, Twist-Bend Nematic, Intercalated Smectic, and Soft Crystalline Mesophases.

Liquid crystalline dimers and dimesogens have attracted significant attention due to their tendency to exhibit twist-bend modulated nematic (N) phases. While the features that give rise to N phase formation are now somewhat understood, a comparable structure-property relationship governing the formation of layered (smectic) phases from the N phase is absent. In this present work, we find that by selecting mesogenic units with differing polarities and aspect ratios and selecting an appropriately bent central spacer we obtain a material that exhibits both N and intercalated smectic phases.

Efficiency improvements in a dichroic dye-doped liquid crystal Fresnel lens.

A dichroic dye-doped liquid crystal Fresnel lens was fabricated and investigated to observe the combination of phase and amplitude modulation based focusing. An anthraquinone dichroic dye was doped into a liquid crystal host, which when in the Fresnel lens configuration, generates a Fresnel zone plate with alternating "transparent" and "opaque" zones. The zones were induced by using photo-alignment of a light-sensitive alignment layer to generate the alternating pattern.

Shape segregation in molecular organisation: a combined X-ray scattering and molecular dynamics study of smectic liquid crystals.

Temperature-dependent X-ray scattering studies have been carried out on 4-undecyloxy-4'-cyanobiphenyl (11OCB) and 4-(12,12-dimethyltridecyloxy)-4'-cyanobiphenyl (t-Bu-11OCB) in the smectic A phase, from which their layer spacings and translational order parameters were obtained. Marked differences between the layer structures of the two compounds were demonstrated, showing that the addition of the t-Bu group results in a higher translational order parameter and wider layer spacing for t-Bu-11OCB than 11OCB. Fully atomistic MD simulations of both compounds run for >1000 ns demonstrated the spontaneous formation of smectic mesophases from isotropic starting geometries, and experimental trends in order parameters and absolute layer spacings were shown to be replicated well.

Molecular Flexibility and Bend in Semi-Rigid Liquid Crystals: Implications for the Heliconical Nematic Ground State.

The N 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 H NOESY NMR, finding good agreement between experiment and computational work.

Order parameters, orientational distribution functions and heliconical tilt angles of oligomeric liquid crystals.

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.

Double helical structure of the twist-bend nematic phase investigated by resonant X-ray scattering at the carbon and sulfur K-edges.

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.

A novel nematic-like mesophase induced in dimers, trimers and tetramers doped with a high helical twisting power additive.

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.

Optically active bimesogens incorporating branched central spacers.

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.

A Nanohelicoidal Nematic Liquid Crystal Formed by a Non-Linear Duplexed Hexamer.

The twist-bend modulated nematic liquid-crystal phase exhibits formation of a nanometre-scale helical pitch in a fluid and spontaneous breaking of mirror symmetry, leading to a quasi-fluid state composed of chiral domains despite being composed of achiral materials. This phase was only observed for materials with two or more mesogenic units, the manner of attachment between which is always linear. Non-linear oligomers with a H-shaped hexamesogen are now found to exhibit both nematic and twist-bend modulated nematic phases.

Molecular shape as a means to control the incidence of the nanostructured twist bend 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.

Combined Microscopy, Calorimetry and X-ray Scattering Study of Fluorinated Dimesogens.

The material FDO11DFCB3 (compound 2 in this work) remains the only example of a liquid-crystalline material to exhibit a phase transition from the heliconical twist-bend phase into a lamellar smectic A mesophase, additionally this material exhibits a previously unidentified mesophase. We have prepared and characterised several homologues of this compound, with each material subjected to an in-depth analysis by optical microscopy, calorimetry and small angle X-ray scattering studies. Despite FDO11DFCB3 being similar in chemical structure to the novel materials presented herein its liquid-crystalline behaviour is rather different, indicating an unexpected sensitivity of the twist-bend phase to molecular structure.

Rational Design of Rod-Like Liquid Crystals Exhibiting Two Nematic Phases.

Recently, a polar, rod-like liquid-crystalline material was reported to exhibit two distinct nematic mesophases (termed N and N ) separated by a weakly first-order transition. Herein, we present our initial studies into the structure-property relationships that underpin the occurrence of the lower-temperature nematic phase, and report several new materials that exhibit this same transformation. We have prepared material with significantly enhanced temperature ranges, allowing us to perform a detailed study of both the upper- and lower-temperature nematic phases by using small-angle X-ray scattering.

Photoswitching of Dihydroazulene Derivatives in Liquid-Crystalline Host Systems.

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.

The Dependency of Nematic and Twist-bend Mesophase Formation on Bend Angle.

We have prepared and studied a family of cyanobiphenyl dimers with varying linking groups with a view to exploring how molecular structure dictates the stability of the nematic and twist-bend nematic mesophases. Using molecular modelling and 1D H NOESY NMR spectroscopy, we determine the angle between the two aromatic core units for each dimer and find a strong dependency of the stability of both the nematic and twist-bend mesophases upon this angle, thereby satisfying earlier theoretical models.

Does Topology Dictate the Incidence of the Twist-Bend Phase? Insights Gained from Novel Unsymmetrical Bimesogens.

We prepared a significant number of unsymmetrical liquid-crystalline dimers that exhibit the twist-bend nematic phase; a state of matter that exhibits spontaneous breaking of mirror symmetry and, for some materials, a microsecond electrooptic response. A number of novel unsymmetrical bimesogens were synthesized and in comparing their thermal behaviour to previous literature examples, we have uncovered an unexpected relationship between the thermal stability of the nematic and N phases. This relationship demonstrates that molecular shape dictates the incidence of this fascinating phase of matter and leads us to speculate as to the existence of "twist-bend nematic phases" on length scales beyond those of the molecule.

Experimental and molecular dynamics studies of anthraquinone dyes in a nematic liquid-crystal host: a rationale for observed alignment trends.

Five anthraquinone dyes with bis(4-propylphenyl) substituents, connected via sulfide or amine linking groups at the 1,5-positions or directly at the 2,6-positions, have been studied as guests in the nematic liquid crystal host, E7. Polarized UV-visible absorption spectra of aligned samples were used to obtain experimental dichroic order parameters, which exhibit values in the range 0.51-0.

Dependence of Mesomorphic Behaviour of Methylene-Linked Dimers and the Stability of the NTB /NX Phase upon Choice of Mesogenic Units and Terminal Chain Length.

Twelve symmetrical dimeric materials consisting of a nonamethylene (C9) spacer and either phenyl 4-(4'-alkylphenyl)benzoate, phenyl 4-(4'-alkylcyclohexyl)benzoate or phenyl 4-(4'-alkylbicyclohexyl)carboxylate mesogenic units were prepared and their mesogenic behaviour characterised by POM, DSC and XRD. All of the materials exhibited nematic phases with clearing points in excess of 200 °C. Four compounds were found to exhibit the twist-bend nematic phase, with one material exhibiting a transition from the NTB phase into an anticlinic smectic 'X' phase.

A Liquid Crystalline Oligomer Exhibiting Nematic and Twist-Bend Nematic Mesophases.

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.

A twist-bend nematic to an intercalated, anticlinic, biaxial phase transition in liquid crystal bimesogens.

In this article we describe for bimesogens the first observed transition from a "heliconical" twist-bend nematic liquid crystal to a novel biaxial, anticlinic, intercalated lamellar phase. The phase behaviour and structures of both polymorphs is similar to that of polymers, confirming that bimesogens can act as model systems for main chain liquid crystal polymers, and in principle are separate soft-matter branches of self-organising systems.

Chiral dopants and the twist-bend nematic phase--induction of novel mesomorphic behaviour in an apolar bimesogen.

Herein we report studies on a bimesogen that exhibits a chiral twist bend nematic phase when doped with small weight percentages of a chiral material and a partial phase diagram constructed. At low concentrations a wide temperature range blue phase is observed, whereas at higher concentrations an additional 'nematic-like' mesophase was discovered at a lower temperature than the twist-bend nematic phase. In addition to an apparent isotropic-"isotropic" transition, the doped materials also exhibited a weakly birefringent phase upon annealing in the isotropic liquid phase, implying pretransitional behaviour in the same vein as that seen for TGB phases.

Dyes in Liquid Crystals: Experimental and Computational Studies of a Guest-Host System Based on a Combined DFT and MD Approach.

Practical applications of guest-host liquid crystal systems are critically dependent on the alignment of the guest species within the liquid crystal host. UV/Vis absorption spectroscopy shows that the 1,5-dihydroxy-2,6-bis-(4-propylphenyl)-9,10-anthraquinone dye aligns within the E7 nematic host, giving an experimental dichroic ratio of 9.40 and dye order parameter of 0.

Apolar bimesogens and the incidence of the twist-bend nematic 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.

Relationship between molecular association and re-entrant phenomena in polar calamitic liquid crystals.

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.