Understanding the twist-bend nematic phase: the characterisation of 1-(4-cyanobiphenyl-4'-yloxy)-6-(4-cyanobiphenyl-4'--yl)hexane (CB6OCB) and comparison with CB7CB

The synthesis and characterisation of the nonsymmetric liquid crystal dimer, 1-(4-cyanobiphenyl-40-yloxy)-6- (4-cyanobiphenyl-40-yl)hexane (CB6OCB) is reported. An enantiotropic nematic (N)–twist-bend nematic (NTB) phase transition is observed at 109 1C and a nematic–isotropic phase transition at 153 1C. The NTB phase assignment has been confirmed using polarised light microscopy, freeze fracture transmission electron microscopy (FFTEM), 2H-NMR spectroscopy, and X-ray diffraction. The effective molecular length in both the NTB and N phases indicates a locally intercalated arrangement of the molecules, and the helicoidal pitch length in the NTB phase is estimated to be 8.9 nm. The surface anchoring properties of CB6OCB on a number of aligning layers is reported. A Landau model is applied to describe high-resolution heat capacity measurements in the vicinity of the NTB–N phase transition. Both the theory and heat capacity measurements agree with a very weak first-order phase transition. A complementary extended molecular field theory was found to be in suggestive accord with the 2H-NMR studies of CB6OCB-d2, and those already known for CB7CB-d4. These include the reduced transition temperature, TNTBN/TNI, the order parameter of the mesogenic arms in the N phase close to the NTB–N transition, and the order parameter with respect to the helix axis which is related to the conical angle for the NTB phase.Postprint (published version

Distinctive dielectric properties of nematic liquid crystal dimers

We provide an overview of the effect of the molecular structure on the dielectric properties of dimers exhibiting nematic and twist-bend nematic phases with special focus on how the conformational distribution changes are reflected by the dielectric behaviour. Nematic dimers show distinctive dielectric properties which differ from those of archetypical nematic liquid crystals, as for example, unusual temperature dependence of the static permittivity or dielectric spectra characterised by two low-frequency relaxation processes with correlated strengths. The interpretation of such characteristic behaviour requires that account is taken of the effect of molecular flexibility on the energetically favoured molecular shapes. The anisotropic nematic interactions greatly influence the conformational distribution. Dielectric behaviour can be used to track those conformational changes due to dependence of the averaged molecular dipole moment on the averaged molecular shape. Results for a number of dimers are compared and analysed on the basis of the influence of details of the molecular structure, using a recently developed theory for the dielectric properties of dimers.Postprint (author's final draft

Miscibility studies of two twist-bend nematic liquid crystal dimers with different average molecular curvatures. A comparison between experimental data and predictions of a Landau mean-field theory for the NTB-N phase transition

We report a calorimetric study of a series of mixtures of two twist-bend liquid crystal dimers, the 1'',7''-bis(4-cyanobiphenyl)-4'-yl heptane (CB7CB) and 1''-(2',4-difluorobiphenyl-4'-yloxy)-9''-(4-cyanobiphenyl-4'-yloxy) nonane (FFO9OCB), the molecules of which have different effective molecular curvatures. High-resolution heat capacity measurements in the vicinity of the NTB-N phase transition for a selected number of binary mixtures clearly indicate a first order NTB-N phase transition for all the investigated mixtures, the strength of which decreases when the nematic range increases. Published theories predict a second order NTB-N phase transition, but we have developed a self-consistent mean field Landau model using two key order parameters: A symmetric and traceless tensor for the orientational order and a short-range vector field which is orthogonal to the helix axis and rotates around of the heliconical structure with an extremely short periodicity. The theory, in its simplified form, depends on two effective elastic constants and explains satisfactorily our heat capacity measurements and also predicts a first-order NTB-N phase transition. In addition, as a complementary source of experimental measurements, the splay (K1) and bend (K3) elastic constants in the conventional nematic phase for the pure compounds and some selected mixtures have been determined.Postprint (author's final draft

Molecular dynamics of a binary mixture of twist-bend nematic liquid crystal dimers studied by dielectric spectroscopy

We report a comprehensive dielectric characterization of a liquid crystalline binary mixture composed of the symmetric mesogenic dimer CB7CB and the nonsymmetric mesogenic dimer FFO9OCB. In addition to the high-temperature nematic phase, such a binary mixture shows a twist-bend nematic phase at room temperature which readily vitrifies on slow cooling. Changes in the conformational distribution of the dimers are reflected in the dielectric permittivity and successfully analyzed by means of an appropriate theoretical model. It is shown that the dielectric spectra of the mixture reflect the different molecular dipole properties of the components, resembling in the present case the characteristic dielectric spectra of nonsymmetric dimers. Comparison of the nematic and twist-bend nematic phases reveals that molecular dynamics are similar despite the difference in the molecular environment.Postprint (author's final draft

Influence of internal flexibility on the double glass transition in a series of odd non-symmetric liquid crystal dimers characterised by dielectric measurements

Dielectric measurements (thermally stimulated depolarisation currents and broadband dielectric spectroscopy) have been performed near the glass transition to study the glass transition on the odd non-symmetric liquid crystal (LC) dimers of the series -(4-cyanobiphenyl-4'-oxy)--(1-pyreniminebenzylidene-4'-oxy) alkanes (CBOnO.Py) with n ranging from 3 to 9. A previous study [S. Diez-Berart et al., Materials 8 (2015) 3334] carried out in CBO11O.Py showed the presence of two glass transition temperatures, attributed to different molecular motions of the terminal groups. The study performed allows us to analyse the molecular dynamics in the rest of the series and determine the role played by the flexible spacer. Parallel and perpendicular orientations of the molecular director with regards to the probe electric field have been investigated. The low and intermediate observed relaxations are explained in the framework of Stocchero's theoretical model [M. Stocchero, J. Chem. Phys. 121 (2004) 8079] for the dielectric behaviour of non-symmetric LCs dimers, as independent end-over-end rotations of each terminal semi-rigid unit. As the length of the spacer chain in the series of compounds decreases, the different relaxations become progressively more coupled at the glass transition. Numerical simulations of the calorimetric response from the obtained kinetic parameters show good agreement with experimental behaviour.Postprint (author's final draft

Twist, tilt, and orientational order at the nematic to twist-bend nematic phase transition of 1 '',9 ''-bis(4-cyanobiphenyl-4 '-yl) nonane: A dielectric, H-2 NMR, and calorimetric study

The nature of the nematic-nematic phase transition in the liquid crystal dimer 1 '',9 ''-bis(4-cyanobiphenyl-4'-yl) nonane (CB9CB) has been investigated using techniques of calorimetry, dynamic dielectric response measurements, and H-2 NMR spectroscopy. The experimental results for CB9CB show that, like the shorter homologue CB7CB, the studied material exhibits a normal nematic phase, which on cooling undergoes a transition to the twist-bend nematic phase (N-TB), a uniaxial nematic phase, promoted by the average bent molecular shape, in which the director tilts and precesses describing a conical helix. Modulated differential scanning calorimetry has been used to analyze the nature of the N-TB-N phase transition, which is found to be weakly first order, but close to tricritical. Additionally broadband dielectric spectroscopy and H-2 magnetic resonance studies have revealed information on the structural characteristics of the recently discovered twist-bend nematic phase. Analysis of the dynamic dielectric response in both nematic phases has provided an estimate of the conical angle of the heliconical structure for the N-TB phase. Capacitance measurements of the electric-field realignment of the director in initially planar aligned cells have yielded values for the splay and bend elastic constants in the high temperature nematic phase. The bend elastic constant is small and decreases with decreasing temperature as the twist-bend phase is approached. This behavior is expected theoretically and has been observed in materials that form the twist-bend nematic phase. H-2 NMR measurements characterize the chiral helical twist identified in the twist-bend nematic phase and also allow the determination of the temperature dependence of the conical angle and the orientational order parameter with respect to the director.Postprint (author's final draft

Order parameters and time evolution of mesophases in the lyotropic chromonic liquid crystal Sunset Yellow FCF by DNMR

Uniaxial order parameters of the nematic and columnar mesophases in the lyotropic chromonic liquid crystal Sunset Yellow FCF have been determined from deuteron nuclear magnetic resonance, where random confinement of the system by the dispersion of aerosil nanoparticles has been performed to help obtain the angular dependent spectra. The long-time evolution study of the order parameters shows that the system requires tens of hours to stabilize after a deep change in temperature, in contrast with the very fast assembly process of the aggregates. Finally, the degree of order of the water molecules, forced by the uniaxial environment, has been determined

Order parameters and time evolution of mesophases in the lyotropic chromonic liquid crystal Sunset Yellow FCF by DNMR

Uniaxial order parameters of the nematic and columnar mesophases in the lyotropic chromonic liquid crystal Sunset Yellow FCF have been determined from deuteron nuclear magnetic resonance, where random confinement of the system by the dispersion of aerosil nanoparticles has been performed to help obtain the angular dependent spectra. The long-time evolution study of the order parameters shows that the system requires tens of hours to stabilize after a deep change in temperature, in contrast with the very fast assembly process of the aggregates. Finally, the degree of order of the water molecules, forced by the uniaxial environment, has been determined

Influence of liquid crystalline phases on the tunability of a random laser

In this paper, we report the temperature behavior of an optimized disordered photonic system-based liquid crystal by means of heat capacity and refractive index measurements. The scattering system is formed by a porous borosilicate glass random matrix (about 60%) infiltrated with a smectogenic liquid crystal (about 16%) and a small amount of laser dye (0.1%). The rest of the scattering system is about 24% air, giving rise to a high refractive index contrast scattering system. Such a system has the functionality to change the refractive index contrast with temperature due to the liquid crystal temperature behavior. The system, optically pumped by the second harmonic of a Q-switched Nd:YAG pulsed laser working at 532 nm, exhibits random laser action, the threshold of which depends upon the liquid crystalline mesophase. Temperatures of existence of the smectic- B phase correspond to the most optimized random laser. In such a mesophase, the transport mean free path has been determined as about 16 µm in a coherent backscattering experiment.Postprint (author's final draft