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

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

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

Cooperative behavior of molecular motions giving rise to two glass transitions in the same supercooled mesophase of a smectogenic liquid crystal dimer

In the present work, a detailed analysis of the glassy behavior and the relaxation dynamics of the liquid crystal dimer a-(4-cyanobiphenyl-4'-yloxy)-¿-(1-pyrenimine-benzylidene-4'-oxy) heptane (CBO7O.Py) throughout both nematic and smectic-A mesophases by means of broadband dielectric spectroscopy has been performed. CBO7O.Py shows three different dielectric relaxation modes and two glass transition (Tg) temperatures: The higher Tg is due to the freezing of the molecular motions responsible for the relaxation mode with the lowest frequency (µ1L); the lower Tg is due to the motions responsible for the two relaxation modes with highest frequencies (µ1H and µ2), which converge just at their corresponding Tg. It is shown how the three modes follow a critical-like description via the dynamic scaling model. The two modes with lowest frequencies (µ1L and µ1H) are cooperative in the whole range of the mesophases, whereas the highest frequency mode (µ2) is cooperative just below some crossover temperature. In terms of fragility, at the glass transition, the ensemble (µ1H+µ2) presents a value of the steepness index and µ1L a different one, meaning that fragility is a property intrinsic to the molecular motion itself. Finally, the steepness index seems to have a universal behavior with temperature for the dielectric relaxation modes of liquid crystal dimers, being almost constant at high temperatures and increasing drastically when cooling the compound down to the glass transition from a temperature about 34TNI.Postprint (author's final draft

Cooperative behavior of molecular motions giving rise to two glass transitions in the same supercooled mesophase of a smectogenic liquid crystal dimer

In the present work, a detailed analysis of the glassy behavior and the relaxation dynamics of the liquid crystal dimer a-(4-cyanobiphenyl-4'-yloxy)-¿-(1-pyrenimine-benzylidene-4'-oxy) heptane (CBO7O.Py) throughout both nematic and smectic-A mesophases by means of broadband dielectric spectroscopy has been performed. CBO7O.Py shows three different dielectric relaxation modes and two glass transition (Tg) temperatures: The higher Tg is due to the freezing of the molecular motions responsible for the relaxation mode with the lowest frequency (µ1L); the lower Tg is due to the motions responsible for the two relaxation modes with highest frequencies (µ1H and µ2), which converge just at their corresponding Tg. It is shown how the three modes follow a critical-like description via the dynamic scaling model. The two modes with lowest frequencies (µ1L and µ1H) are cooperative in the whole range of the mesophases, whereas the highest frequency mode (µ2) is cooperative just below some crossover temperature. In terms of fragility, at the glass transition, the ensemble (µ1H+µ2) presents a value of the steepness index and µ1L a different one, meaning that fragility is a property intrinsic to the molecular motion itself. Finally, the steepness index seems to have a universal behavior with temperature for the dielectric relaxation modes of liquid crystal dimers, being almost constant at high temperatures and increasing drastically when cooling the compound down to the glass transition from a temperature about 34TNI

Planning London's transport

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Bent-rod liquid crystal dimers: synthesis and mesomorphic properties

The synthesis and characterization of three bent-rod dimers are reported. Very long flexible spacers that include methylene units and either a phenyl ring or a triazole moiety as connecting structures join the bent-and rod-promesogenic cores. Polarizing microscopy, modulated differential scanning calorimetry, X-ray diffraction at variable temperature and dielectric measurements have been performed to establish the mesophase behaviour of the dimers. The results show a complex supramolecular organization for this kind of flexible dimer in the mesophase. Interestingly, the length and the chemical nature of the flexible linking spacers condition the liquid crystalline properties of these novel compounds. Additionally, it has been found that the chemical structure of the rod-like core plays a key role in determining the kind of mesophase, either nematic or lamellar, formed by these materials

Dispersion of gamma-alumina nano-sized spherical particles in a calamitic liquid Crystal. Study and optimization of the confinement effects

We report an experimental study on confined systems formed by butyloxybenzylidene octylaniline liquid crystal (4O.8) + gamma-alumina nanoparticles. The effects of the confinement in the thermal and dielectric properties of the liquid crystal under different densities of nanoparticles is analyzed by means of high resolution Modulated Differential Scanning Calorimetry (MDSC) and broadband dielectric spectroscopy. First, a drastic depression of the N-I and SmA-N transition temperatures is observed with confinement, the more concentration of nanoparticles the deeper this depression is, driving the nematic range closer to the room temperature. An interesting experimental law is found for both transition temperatures. Second, the change in shape of the heat capacity peaks is quantified by means of the full width half maximum (FWHM). Third, the confinement does not noticeably affect the molecular dynamics. Finally, the combination of nanoparticles and the external applied electric field tends to favor the alignment of the molecules in metallic cells. All these results indicate that the confinement of liquid crystals by means of gamma-alumina nanoparticles could be optimum for liquid crystal-based electrooptic devices

Bent-rod liquid crystal dimers: synthesis and mesomorphic properties

The synthesis and characterization of three bent-rod dimers are reported. Very long flexible spacers that include methylene units and either a phenyl ring or a triazole moiety as connecting structures join the bent-and rod-promesogenic cores. Polarizing microscopy, modulated differential scanning calorimetry, X-ray diffraction at variable temperature and dielectric measurements have been performed to establish the mesophase behaviour of the dimers. The results show a complex supramolecular organization for this kind of flexible dimer in the mesophase. Interestingly, the length and the chemical nature of the flexible linking spacers condition the liquid crystalline properties of these novel compounds. Additionally, it has been found that the chemical structure of the rod-like core plays a key role in determining the kind of mesophase, either nematic or lamellar, formed by these materials

Dispersion of gamma-alumina nano-sized spherical particles in a calamitic liquid Crystal. Study and optimization of the confinement effects

We report an experimental study on confined systems formed by butyloxybenzylidene octylaniline liquid crystal (4O.8) + gamma-alumina nanoparticles. The effects of the confinement in the thermal and dielectric properties of the liquid crystal under different densities of nanoparticles is analyzed by means of high resolution Modulated Differential Scanning Calorimetry (MDSC) and broadband dielectric spectroscopy. First, a drastic depression of the N-I and SmA-N transition temperatures is observed with confinement, the more concentration of nanoparticles the deeper this depression is, driving the nematic range closer to the room temperature. An interesting experimental law is found for both transition temperatures. Second, the change in shape of the heat capacity peaks is quantified by means of the full width half maximum (FWHM). Third, the confinement does not noticeably affect the molecular dynamics. Finally, the combination of nanoparticles and the external applied electric field tends to favor the alignment of the molecules in metallic cells. All these results indicate that the confinement of liquid crystals by means of gamma-alumina nanoparticles could be optimum for liquid crystal-based electrooptic devices