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 H2 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 (NTB), 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 NTB-N phase transition, which is found to be weakly first order, but close to tricritical. Additionally broadband dielectric spectroscopy and H2 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 NTB 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. H2 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

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

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

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

Synthesis and properties of (+/-)-trans-([small eta]2-alkene)(4-alkyloxy-4[prime or minute]-stilbazole)dichloroplatinum: a remarkable family of low-melting metallomesogens

none5A novel series of low-melting metallomesogens (metal-containing liquid crystals) has been prepared and characterised. Reaction of Zeise{'}s salt K[PtCl([small eta]-CH[double bond{,} length half m-dash]CH)] with the 4--alkyloxy-4[prime or minute]-stilbazole ligands (L = CHOCHCH[double bond{,} length half m-dash]CHCHN; = 3-12) yielded -[PtCl([small eta]-CH[double bond{,} length half m-dash]CH)L]{,} which react with alk-1-enes (CH[double bond{,} length half m-dash]CHCH; = 1-8{,} 10 or 12) to give -[PtCl(CH[double bond{,} length half m-dash]CHCH)L]. The complexes where ()[gt-or-equal] 8 are generally liquid crystalline (smectic A mesophases); those with shorter tails [()= 8 to 13] show monotropic mesophases{,} while those with longer tails [() > 13] show enantiotropic behaviour. The melting temperatures are lower than would be anticipated for metallomesogens of this size{,} reflecting the non-centrosymmetric molecular structures which make the crystal packing less easy. A 70 : 30 mixture of the complexes (= 12{,} = 3; K [rightward arrow] S at 61 [degree]C) and (= 12{,} = 6; K [rightward arrow] S at 70 [degree]C) shows the transition into the mesophase{,} K [rightward arrow] S{,} at 45 [degree]C{,} an unusually low temperature. The mesophase to isotropic (S[rightward arrow] I) transition temperatures remain rather constant at 92 +/- 4 [degree]C for all compositions.J. P. Rourke;F. P. Fanizzi;D. W. Bruce;D. A. Dunmur;P. M. MaitlisJ. P., Rourke; Fanizzi, Francesco Paolo; D. W., Bruce; D. A., Dunmur; P. M., Maitli

Molecular theory of dielectric relaxation in nematic dimers

This paper reports a theory for the dielectric relaxation of dimeric mesogenic molecules in a nematic liquid crystal phase. Liquid crystal dimers consist of two mesogenic groups linked by a flexible chain. Recent experimental studies [D. A. Dunmur, G. R. Luckhurst, M. R. de la Fuente, S. Diez, and M. A. Perez Jubindo, J. Chem. Phys. 115, 8681 (2001)] of the dielectric properties of polar liquid crystal dimers have found unexpected results for both the static (low frequency) and variable frequency dielectric response of these materials. The theory developed in this paper provides a quantitative model with which to understand the observed experimental results. The mean-square dipole moments of alpha, omega-bis[(4-cyanobiphenyl-4'-yl]alkanes in a nematic phase have been calculated using both the rotational isomeric state model and a full torsional potential for the carbon-carbon bonds of the flexible chain. The orienting effect of the nematic phase is taken into account by a parametrized potential of mean torque acting on the mesogenic groups and the segments in the flexible chain. Results of calculations using the full torsional potential are in excellent agreement with experimental results for comparable systems. The probability density p(eq)(beta(A),beta(B)) for the orientation of the mesogenic groups (A,B) along the nematic director is also calculated. The resultant potential of mean torque is a surface characterized by four deep energy wells or sites equivalent to alignment of the terminal groups A and B approximately parallel and antiparallel to the director; of course, the reversal of the director leads to equivalent sites. This potential energy surface provides the basis for a kinetic model of dielectric relaxation in nematic dimers. Solution of the Fokker-Planck equation corresponding to this four-site model gives the time dependence of the site populations, and hence the time-correlation functions for the total dipole moment along the director. In this model the end-over-end rotation of the molecule, corresponding to simultaneous reversal of both mesogenic groups, is excluded because the activation energy is too large. Results are presented for a number of cases, in which a dipole is located on one or both of the mesogenic groups, and additionally where the groups differ in size. For the latter, under particular conditions, the correlation function exhibits a biexponential decay, which corresponds to two low frequency absorptions in the dielectric spectrum. This is exactly what has been observed for nonsymmetric nematic dimers having different groups terminating a flexible chain. Experimental results over a range of temperature for the nonsymmetric dimer alpha-[(4-cyanobiphenyl)-4'-yloxy]-omega-(4-decylanilinebenzylidene-4'-o xy)nonane can be fitted precisely to the theory, which provides new insight into the orientational and conformational dynamics of molecules in ordered liquid crystalline phases

trans-(į2-Alkene)(4'-alkyloxy-4-stilbazole)dichloro-platinum; Low Melting Organometallic Mesogens

-[PtCl(CHOCHCH[double bond{,} length half m-dash]CHCHN)([small eta]-CH[double bond{,} length half m-dash]CHCH)]() form stable smectic A mesophases on heating (for [gt-or-equal]7{,} [gt-or-equal]7; [gt-or-equal]8{,} [gt-or-equal]5; [gt-or-equal]9{,} [gt-or-equal]2; and [gt-or-equal]11{,} [gt-or-equal]0); melting temperatures below 50 [degree]C can easily be achieved

On the investigation of field-induced director dynamics: a novel ESR experiment

The rotational viscosity coefficient of a nematic liquid crystal with a positive diamagnetic susceptibility anisotropy can be determined by monitoring the time dependence of the director orientation as it is rotated by a field from a non-equilibrium to the equilibrium state parallel to the field. A variety of techniques is available using different properties to monitor the director orientation as a function of time. Normally these experiments are designed so that the property used to determine the director orientation does not change during the time taken for its measurement. Here using ESR spectroscopy, we explore the benefits of exploiting exactly the opposite situation. That is during the time taken to record the ESR spectrum the director orientation is allowed to change. We have developed both semi-quantitative and quantitative models to allow us to simulate how the form of the spectrum depends on experimental conditions such as the field scan rate. These models have also proved to be valuable in designing the experiment and in analysing the spectra. It seems that this novel ESR experiment provides a valuable route to the field-induced relaxation time and hence to the rotational viscosity coefficient