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 ca. +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). DFT-optimised structures were calculated for between 1 and 16 conformers/tautomers of each dye, and their relative energies, UV-visible absorption wavelengths, oscillator strengths, transition dipole moments, molecular surface tensors and quadrupole tensors were obtained and used in subsequent calculations. A simple approach provided calculated UV-visible absorption spectra of the dyes that gave a qualitative match with the experimental spectra, and the calculated peak positions showed a linear correlation with the experimental values across the full visible range of ca. 350-700 nm. A short-range, shape-based, mean-field orienting potential based on the calculated surface tensors was combined with the calculated transition dipole moment vectors to give calculated dichroic ratios of the dyes that showed a linear correlation across the full range of experimental values. A modification of this mean-field orienting potential to include a long-range, electrostatic component based on the calculated quadrupole tensors gave a slightly improved linear correlation but a slightly worse overall match to the experimental values. The results show that short-range, shape-based interactions dominate the orienting potential for the systems studied here, with the inclusion of long-range quadrupole interactions providing a slightly better model for only some of the dyes. Overall, the use of a mean-field approach allied with molecular properties that can be calculated with relative ease and low computational expense has provided calculated peak positions and dichroic ratios that show good matches and correlations with experimental data from a variety of dye structures without the need to input any experimental data from the dyes. Hence, this method may provide a general and rapid approach to predicting the optical properties of dyes in liquid crystal hosts, enabling candidate dye structures to be screened prior to synthesis.

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 (NTB) phases. While the features that give rise to NTB phase formation are now somewhat understood, a comparable structure-property relationship governing the formation of layered (smectic) phases from the NTB 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 NTB and intercalated smectic phases. The higher temperature smectic phase is assigned as SmCA based on its optical textures and X-ray scattering patterns. A detailed study of the lower temperature smectic ''X'' phase by optical microscopy and SAXS/WAXS demonstrates this phase to be smectic, with an in-plane orthorhombic or monoclinic packing and long (>100 nm) out of plane correlation lengths. This phase, which has been observed in a handful of materials to date, is a soft-crystal phase with an anticlinic layer organisation. We suggest that mismatching the polarities, conjugation and aspect ratios of mesogenic units is a useful method for generating smectic forming dimesogens.

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. The voltage dependency of efficiency for the dye-doped and pure liquid crystal Fresnel devices were investigated. Incorporation of dyes into the device yielded a significant 4% improvement in relative efficiency in the lens, giving a maximum of 37% achieved in the device, much closer to the theoretical 41% limit when compared with the non-dye-doped device. The input polarization dependence of efficiency was also investigated, showing very small fluctuations (±1.5%), allowing further insight into the effect of fabrication method on these liquid crystal Fresnel devices.

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. Further analysis showed that both the aromatic head-groups and the alkyl tail-groups exhibit interdigitation in the simulated smectic phases of both compounds, and the difference in the layer structures between 11OCB and t-Bu-11OCB could be attributed mainly to a shape segregation effect arising from the addition of the bulky t-Bu end-group to the alkyl chain.

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

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 1 H 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.

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. 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.

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. 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.

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. This shatters the assumption that a linear sequence of mesogenic units is a prerequisite for this phase, and points to this state of matter being exhibited by a wider range of self-assembling structures than was previously envisaged. These results support the double helix model of the TB phase as opposed to the simple heliconical model. This new class of materials could act as low-molecular-weight surrogates for cross-linked liquid-crystalline elastomers.

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. 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.

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 0.36 and 0.35 µm-1 wt%-1 respectively. Compound 1 exhibited a monotropic chiral nematic phase, however no twist-bend modulated phase was observed. We prepared a number of analogues of 1 incorporating different mesogenic units and observe that those with a small aspect ratio are non mesogenic, whereas those with larger aspect ratios variously exhibit chiral nematic, TB, SmC and SmB phases.

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 NX ) 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. We observed a continuous change in d spacing rather than a sharp change at the phase transition, a result consistent with a transition between two nematic phases, structures of which are presumably degenerate.

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. 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.

Principal molecular axis and transition dipole moment orientations in liquid crystal systems: an assessment based on studies of guest anthraquinone dyes in a nematic host.

An assessment of five different definitions of the principal molecular axis along which molecules align in a nematic liquid crystal system has been made by analysing fully atomistic molecular dynamics (MD) simulations of a set of anthraquinone dyes in the cyanobiphenyl-based nematic host mixture E7. Principal molecular axes of the dyes defined by minimum moment of inertia, minimum circumference, minimum area, maximum aspect ratio, and surface tensor models were tested, and the surface tensor model was found to give the best description. Analyses of MD simulations of E7 alone showed that the surface tensor model also gave a good description of the principal molecular axes of the host molecules, suggesting that this model may be applicable more generally. Calculated dichroic order parameters of the guest-host systems were obtained by combining the surface tensor analysis with fixed transition dipole moment (TDM) orientations from time-dependent density functional theory (TD-DFT) calculations on optimised structures of the dyes, and the trend between the dyes generally matched the trend in the experimental values. Additional analyses of the guest-host simulations identified the range of conformers explored by the flexible chromophores within the dyes, and TD-DFT calculations on corresponding model structures showed that this flexibility has a significant effect on the TDM orientations within the molecular frames. Calculated dichroic order parameters that included the effects of this flexibility gave a significantly improved match with the experimental values for the more flexible dyes. Overall, the surface tensor model has been shown to provide a rationale for the experimental alignment trends that is based on molecular shape, and molecular flexibility within the chromophores has been shown to be significant for the guest-host systems: the computational approaches reported here may be used as a general aid in the predictive design of dyes with appropriate molecular shapes and flexibilities for guest-host 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 1H 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 NTB 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 0.51-0.74. Fully atomistic MD simulations of these guest-host systems were carried out, generally using default parameters but using new force constants derived here for the dyes containing flexible phenyl-sulfide and phenyl-amine linking groups. An analysis of the alignment of the dye molecules in these simulations provides calculated molecular order parameters, which are combined with calculated order parameters for the alignment of the transition dipole moments within the dyes, reported previously, to give calculated dichroic order parameters. The trend in the calculated dichroic order parameters between the dyes shows a good match with the trend in the experimental values, enabling the observed variation to be rationalised primarily by changes in the alignment of the calculated transition dipole moments within the dyes; the calculated molecular order parameters show a relatively small variation between the dyes. The results indicate that this computational approach may be used generally to rationalise trends in the alignment of guest molecules in liquid crystal hosts, suggesting that it may also be able to provide a predictive aid in the design of guest dyes.

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. Across all three series of compounds the length of terminal chain is seen to dictate, to some degree, the type of mesophase formed: shorter terminal chains favour nematic and NTB mesophases, whereas longer terminal aliphatic chains were found to promote smectic phases.

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.