On the Influence of Elastic Modes on the N.M.R. Lineshapes of Polymer Liquid Crystals

We have studied the influence of thermally excited orientational fluctuations on the N.M.R. lineshape of a nematic monodomain. The influence is characterized by a static order parameter S_stat whose theoretical expression in terms of viscoelastic parameters is derived. This model is applied to the proton N.M.R. spectrum of a thermotropic main chain polymer. The values of S_stat are deduced from the study of the changes of the N.M.R. lineshape as a function of the angle between the static magnetic field and the nematic director. Good agreement is obtained with theoretical values calculated using estimated values of the Leslie viscosity coefficients and the Frank elastic constants. The importance of an accurate knowledge of S_stat for a number of problems is stressed.     

N.M.R. study of segmental molecular interactions in liquid crystals

Abstract

A simple statistical model of interacting non-rigid molecules, based on a perturbation expansion of the pair correlation function and the additivity of segmental interactions, is applied to the study of orientational order as measured by N.M.R. in the nematic and S_A phases of 4-n-alkyl-4′-cyanobiphenyls (N-CB, N = 5 to 8), the nematic and S_C phases of 4-n-alkyloxybenzoic acids (N-OBA, N = 7, 8) and the D _h0 columnar discotic phase of hexa-alkyloxytriphenylenes (N-THE, N = 5 to 8). The order parameters of each homologous series are correctly described in terms of two isotropic and two anisotropic segmental coupling constants. The model predicts certain relations among coupling constants pertaining to different homogous series. These predictions are supported by the results obtained for the three types of compounds studied.     

Orientational ordering of 4-substituted phenylcyclohexanes studied by carbon-13 two-dimensional N.M.R.

Abstract

An N.M.R. method combining the techniques of separated local field spectroscopy (SLF) and variable angle spinning (VAS) is valuable in the investigtion of nematic liquid crystals. Rapid sample spinning causes the nematic director to align along the spinning axis, resulting in narrow peaks in the C-13 N.M.R. spectrum. SLF is a two-dimensional N.M.R. method which produces a first order splitting pattern for each carbon signal from which C–H dipolar coupling constants can be determined. The order parameters for all segments of the liquid crystal molecule can then be calculated. Results for three 4′-cyanophenylcyclohexanes are considered here. These compounds are trans-substituted at the 4 position of cyclohexane ring with n-pentane (PCH5), 1-pentene (3d ₁CP) and 3-pentene (1d ₃CP), respectively.     

E.S.R. and D.S.C. investigations of phase transitions in polymorphic 4-n-alkoxybenzylidene-4′-n-alkylanilines

Abstract

It is shown that the McMillan parameter M = T _SAN/T _N1 (where T _SAN and T _NI are respectively the temperatures of the smectic A to nematic (SAN) and the nematic to isotropic (NI) phase transitions) is useful in analysing the crossover between second and first order behaviour of the S_NN transition in the nO.m homologous liquid crystal series (the 4-n-alkoxybenzylidene-4′-n-alkylanilines). Using a phase diagram of orientational ordering versus M for this series, as obtained in this work (from E.S.R. and D.S.C), a symmetric tricritical point with mean field exponent β₂ = 1 is demonstrated. In a preliminary study of E.S.R. linewidth parameters B and C of nitroxide spin probes dissolved in members of the nO.m series exhibiting a first order S_AN transition, critical-type divergences are observed near this transition. In the case where M is closer to 0.959 (the value at the tricritical point), these divergences appear similar to those previously observed in related nO.m members with a second order S_AN transition; however, they are considerably enhanced for an M value closer to unity (i.e. more removed from the tricritical point). This indicates the importance of coupling between orientational and positional order parameters in the observed critical-type divergences.     

Proton N.M.R. lineshape in nematic microdroplets

The dependence of the proton N.M.R. absorption spectrum on nematic director configuration and molecular self-diffusion in nematic submicrondroplets is analysed. The lineshape is evaluated numerically for radial and bipolar director configuration. The motional averaging is taken into account by means of a numerical simulation of the molecular diffusion which induces slow molecular reorientations due to non-uniform orientational ordering in the droplet. This diffusion process strongly affects the absorption spectra of the radial configuration, whereas spectra of the bipolar configuration are only slightly influenced. The possibility of determinating the submicrometre nematic droplet structures using the proton N.M.R. lineshape is discussed.     

Proton N.M.R. lineshape in nematic microdroplets

The dependence of the proton N.M.R. absorption spectrum on nematic director configuration and molecular self-diffusion in nematic submicrondroplets is analysed. The lineshape is evaluated numerically for radial and bipolar director configuration. The motional averaging is taken into account by means of a numerical simulation of the molecular diffusion which induces slow molecular reorientations due to non-uniform orientational ordering in the droplet. This diffusion process strongly affects the absorption spectra of the radial configuration, whereas spectra of the bipolar configuration are only slightly influenced. The possibility of determinating the submicrometre nematic droplet structures using the proton N.M.R. lineshape is discussed.     

1H NMR studies on thioamides: Barriers to internal rotation

The barrier to the internal rotation of the dimethylamino group in thioamides of structure R? CS? N(CH₃)₂, R being (CH₃)₂,N? CS? , CH₃O₂C? or N?C? , is studied by proton magnetic resonance, using the lineshape analysis method of Nakagawa. In the solvents o-dichlorobenzene, naphthalene and nitrobenzene all ΔG≠ values are in the range of 23 to 24 kcal/mol. In these solvents the E_a and ΔS≠ values of each product are linearly related to the dielectric constants.     

On the structure and the chain conformation of side-chain liquid crystal polymers

Abstract

Backbone anisotropy and the structure of the mesophases of a series of side-chain liquid crystal polymers have been studied in the bulk by neutron scattering. The backbone conformation is obtained by small-angle neutron scattering on mixtures of hydrogenous polymers with deuteriated backbones. The components of the radius of gyration parallel, R _⊥ and perpendicular, R ∥ to the magnetic field are determined as a function of temperature for both the nematic phase and the smectic phase. It is shown that the polymer backbone is deformed in both phases. When the polymer exhibits only a nematic phase, it adopts a prolate conformation, where the average backbone direction is more or less parallel to the aligned mesogenic groups. Upon transition from the smectic phase to a nematic phase, the backbone in the nematic phase assumes a slightly oblate shape. This tendency towards oblate shape is due to the smectic fluctuations which are always present in such nematic phases. The exentricity of the oblate backbone conformation in the smectic phase is always larger than in the nematic phase. This is attributed to a periodic distribution of the backbone between the mesophase layers. Then, the backbone anisotropy depends not only on the smectic structure (S_A1, S_Ad), but also on the temperature dependence of the density of aligned mesogenic groups in the layers. On the other hand, it is shown that the isotopic mixtures are no longer ideal when polymers deuteriated in the mesogenic moieties are mixed with the corresponding hydrogenous polymers.     

The heat capacity of the doubly reentrant mesogen: 4-cyanobenzoyloxy-4′-octylbenzoyloxy-p-phenylene

Abstract

Heat capacity of a 20 g sample of the mesogen 4-cyanobenzoyloxy-4′-octylbenzoyloxy-p-phenylene was measured in the temperature range 380 to 510 K by adiabatic calorimetry. The C _p versus T data is interpreted in terms of thermodynamically equivalent S_A1 and S_Ad phases whose Gibbs potential surface intersects the thermodynamically equivalent reentrant nematic and nematic Gibbs potential surface in such a way as to define the first order doubly reentrant phase sequence: S_A1-N-S_Ad-N. The data do not allow any precise estimates of transition enthalpies.     

Study of internal ring rotation and molecular reorientation in the liquid crystal 5O.7 by deuterium N.M.R. spectroscopy

Abstract

The spectral densities of motion were determined by deuterium N.M.R. relaxation measurements in the nematic, smectic A and smectic C phases of 4-n-pentyloxybenzylidene-d ₁-4′-heptylaniline and 4-n-pentyloxybenzylidene-4′-heptylaniline-2,3,5,6-d ₄. By examining two atomic sites on a 5O.7 molecule, we were able to gain information on the reorientation motion and internal rotation of the aniline ring. It was also found that director fluctuations make some contribution to the spectral density J ₁ (ω). We use the superimposed rotations model to account for the internal ring motion and the small step rotational diffusion model for the molecular reorientation. The derived rotational diffusion constants for the spinning and tumbling motions appear to give physically plausible activation energies in the mesophases of 5O.7.     

Thermotropic ionic liquid crystals of pyridinium octylphosphate A N.M.R. and X-ray study

Abstract

A thermotropic ionic lamellar phase from non-stoichiometric pyridinium octyl-phosphates has been investigated by multinuclear N.M.R. and X-ray diffraction. At room temperature and above, this phase is formed for pyridine to octylphosphoric acid molar ratios from 0.2 to 0.8.²H and ¹³C relaxation experiments show that the pyridinium ion undergoes a very anisotropic motion with D_zz > D_xx ? D_yy, z and x being the perpendicular direction to the ring and the c ₂ symmetry axis, respectively. The order parameters given by the ²H quadrupolar splittings and the ¹³C chemical shift anisotropy (CSA) are S_zz = 0.13, S_yy = -0.08 and S_xx = -0.05, showing that the pyridinium ring is preferentially oriented parallel to the lamellar plane. The ³¹P CSA and the C1-P dipolar splitting yield S_zz = 0.33 and S_xx ? S_yy for the octylphosphate anion. The order parameters of alkyl C-H bonds have been obtained from the J resolved two-dimensional ¹³C N.M.R. spectra of oriented samples. Two limiting conformational models have been considered to calculate the S _CH. One of them is reasonably consistent with the structure derived from X-ray experiments and has been used to calculate the dipolar ³¹P relaxation. Taking into account the CSA contribution, the relaxation measurements performed at 36, 121 and 202 MHz show that the octylphosphate anion undergoes a quasi-axial reorientation about the long molecular axis x with D∥/D⊥ = 4 and D⊥ ? 10⁷ rad/s at 300 K.     

A convenient synthesis and the mesomorphic properties of new chiral ferroelectric thiobenzoates

A secondary chiral (R)-(?)-2-alcohol underwent the Mitsunobu reaction with triphenylphosphine, diethyl azodicarboxylate and ethyl 4-hydroxybiphenylcarboxylate, resulting in the desired (S)-(+)-product with high enantiomeric purity (>99% ee), with the chiral branched chain attached to the biphenyl. This method is operationally simple and provides the very important chiral precursor in good yields (62% in dry THF and 72% in dry Et₂O). The condensation of the (S)-(+)-acid chloride from this material and a suitable 4-n-alkylthiophenol in toluene in the presence of pyridine or triethylamine furnishes the chiral (S)-(+)-thiobenzoate liquid crystals in good yields (80–83% in pyridine and 65–68% in Et₃N). (S)-(+)-4-(1-Methylheptyloxy)biphenyl 4-alkylthiobenzoates are abbreviated (S)-MHOBSn , where n varies from 4 to 10 and denotes the number of carbon atoms in the alkyl chain. DSC, polarizing microscopy and X-ray diffraction showed that the (S)-MHOBSn series possesses a rich phase polymorphism: two highly ordered tilted phases CrG* and SmI*, as well as the ferroelectric smectic C (SmC*) and chiral nematic (N*) phase. In this series, the seldom observed transition between the chiral phases SmI*–SmC* is seen. All the compounds possess stable enantiotropic SmC* and N* phases. The existence of weak intermolecular hydrogen-bonding in (S)-MHOBSn was confirmed by FTIR spectroscopy.     

Mesogenic random copolymers. II. Copolymers with one flexible and two rigid segments

We have investigated copolyesters based on a single aliphatic dibasic acid flexible segment and two rigid segments arising from 4,4′-dihydroxybiphenyl (PB) and 2,6-dihydroxynaphthalene (PN). Homopolyesters based on the latter rigid segment exhibit no enantiotropic mesophase for 5 ≤ n ≤ 8. The copolymers are designated PBN-n where n is the number of methylene units in the dibasic acid. From the temperature–composition phase diagram, the odd-membered PBN-5 and PBN-7 exhibit only a nematic phase. The temperature range of the nematic phase decreases progressively with increasing mole fraction of naphthalene units. The even-membered PBN-6 and PBN-8 exhibit a smectic S_H mesophase and a newly induced nematic phase. Comparison with a previous study of copolymers involving a single rigid segment and two flexible segments reveals that the smectic S_H phase is more easily disrupted, and converted to a less ordered nematic phase, by different rigid segments than by different flexible segments. The isotropization entropy of a series of nematogenic equimolar copolymers exhibits a marked odd–even effect, with the observed ΔS_NI values being quite large for the even-membered copolymers.     

Reduced odd–even effects in liquid crystalline carbonate dimers: molecular field analysis

Four liquid crystalline carbonate dimers DCn containing the dimethylbenzalazine mesogen, bis(oxycarbonyloxy)alkane flexible spacers with three to six methylene units and acetate terminal groups were synthesised and their mesogenic behaviour investigated. As compared with the corresponding ester dimers a strong reduction of odd–even fluctuations of nematic–isotropic (N–I) transition entropy is observed. A theoretical analysis of the dimers within the rotational isomeric states (RIS) mean-field approach is also reported. A satisfying agreement between calculated and observed thermodynamic properties is obtained. In fact, the theoretical analysis correctly predicts a significant reduction of the odd–even fluctuations for the core order parameter S as well as for the nematic to isotropic transition entropy △S_NI . The calculated distributions of conformers also show reduced differences between even and odd members. In particular, for even dimers the calculated fraction of linear extended conformers in the nematic phase at the N–I transition is around 27%, which is far below that of the corresponding ester dimers (46%).     

On the conformational effects of intermolecular interactions in nematics

Abstract

A perturbation expansion of the pair correlation function is used to derive the molecular field self-consistency equations for non-rigid molecules. The order parameters and the thermodynamic functions are expressed directly in terms of the segmental interaction coupling constants. The values of these constants for the 4-n-alkyl-4'-cyanobiphenyis (NCB) are determined by analysing the orientational order parameters observed by N.M.R. in the nematic phase; they are in reasonable agreement with values obtained from calculations of the nematic-isotropic transition temperatures. It is found that contributions of the isotropic intermolecular interactions to the conformational energy of the alkyl chain are comparable in magnitude to the direct intramolecular contributions.     

Mesophase stability in binary mixtures of monotropic nematogens

Binary phase diagrams were constructed from laterally substituted methyl azo/ester derivatives, namely 4-(4″-substituted phenylazo)-3-methyl phenyl-4″-alkoxy benzoates (In_a–d). In this group of compound the unsubstituted and chloro-substituted derivatives possess the nematic phase monotropically, while the nitro and methyl analogues are enantiotropically nematogenic. The binary phase diagrams constructed were made once from the monotropic nematogens with each other, and another with the enantiotropic nematogens. In both the cases enantiotropic nematic phase was observed that covers a wide range of composition. The mesophase behaviour of all binary mixtures was investigated by differential scanning calorimetry (DSC) and polarised light microscopy (PLM). The nematic phase was exhibited in all binary mixtures. Independent of the alkoxy chain length, the entropy change, ΔS_N–I of the N–I transition of pure components was found to vary irregularly with the anisotropy of polarisability (?α_X) of the polar substituent, X.     

Some N.M.R. experiments using lyotropic nematic liquid crystals

Abstract

A series of lyotropic nematic liquid crystals based on aniso-dimensional micelles can be subdivided according to micelle shape and diamagnetic susceptibility anisotropy. The proton magnetic resonance spectra of benzene dissolved in dilute solution in several of these phases have been analysed. The signs of the partially averaged dipole–dipole coupling give information about the relative alignment of the six-fold symmetry axis of benzene, the director and the magnetic field. The system caesium perfluorooctanoate/water is unusual in two respects. The system forms a nematic phase with only a binary mixture and the disk micelles align in a perpendicular plane to the magnetic field. As a result the binary system has been studied previously in some detail (see N. Boden, S. A. Come and K. W. Jolley, 1987, J. phys. Chem. 91, 4092). New measurements on the interesting phase diagram have been accomplished using caesium-133 and deuterium magnetic resonance measurements at various temperatures. Some dilatometric measurements have been made to complement the N.M.R. studies.     

A continuum description for cholesteric and nematic twist-bend phases based on symmetry considerations

ABSTRACT

The recently discovered twist-bend nematic phase, N_tb, is a non-uniform equilibrium nematic phase that presents a spontaneous bend with a precession of the nematic director, n, on a conical helix with a tilt angle θ and helical pitch P. The stability of the N_tb phase has been recently demonstrated from the elastic point of view by extending the Frank elastic energy density of the nematic phase to include the symmetry element of the helical axis, t. In the present article, we investigate the influence of an external bulk field (magnetic or electric) on the N_tb phase. Using symmetry arguments we derive the expression for the flexoelectric polarisation in twist-bend nematic phases. We show that, besides the standard contribution related to the spatial variation of the nematic director, two new contributions connected with the existence of the helical axis appear. In the ground state, where the nematic deformation is a pure heliconical deformation, the new contribution vanishes identically, and the total flexoelectric polarisation is perpendicular to the nematic director. Furthermore, as an example, we study the role of an external magnetic field applied parallel to the helical axis for a material with positive magnetic susceptibility anisotropy. We show that the field modifies the range of values of the coupling parameter between the director and the helical axis, thus shifting the interval of values for which this coupling results in the N_tb phase.     

Dielectric relaxation of a short molecule in a liquid-crystalline solvent

Abstract

Dielectric relaxation measurements of 5 mole % 4-n-hexyloxycyanobenzene (I) dissolved in 4-n-pentyloxyphenyl-trans-4-n-octylcyclohexylcarboxylate (II) were carried out from 1 kHz to 10 MHz in the nematic, smectic A and smectic B phases. The relaxation frequency of I parallel to the director is about 05 MHz in the S_Bphase and increases rapidly at the transition from S_B to S_A.     

The dynamics of the CH3CN molecule in the isotropic phase and in a nematic solution

Abstract

NMR lineshape studies of acelonitrile in the isotropic and the liquid-crystalline nematic phase of PCH have been performed. The scalar relaxation of the second kind due to the presence of the ¹⁴N quadrupolar nucleus has been confirmed as the most important relaxation mechanism for this molecule in both the isotropic and the anisotropic phase. It has been found largely responsible for the selective broadening on ¹³C and ¹H transitions. A minor contribution arising from intramolecular dipolar relaxation mechanism has also been investigated. Linewidth analysis of the NMR spectra allowed us to determine the quadrupolar relaxation time T _IN of the ¹⁴N nucleus. This is connected to the correlation time for rotational diffusion perpendicular to the molecular symmetry axis. A possible explanation of a residual selective broadeining which effects the ¹³C and ¹H NMR transitions and is not taken into account by this mechanism, is also given.