Phase-transition studies of 5O.5 and 9O.4

As part of our detailed comparative studies of groups of liquid-crystalline compounds that belong to a homologous series, we present phase-transition studies of the compounds N-(4-n-pentyloxybenzylidene)4'-n-pentylaniline (5O.5) and N-(4-n-nonyloxybenzylidene)4'-n-butylaniline (9O.4) using different experimental techniques. The compound 5O.5 is reported to exhibit a phase sequence N, S_A, S_C, S_B and S_G, while 90.4 shows the sequence S_A, S_F and S_G. The salient features of our work on 5O.5 are (i) a new smectic F phase is found in place of the reported smectic B phase, which is confirmed by both miscibility and X-ray studies; (ii) the formation of smectic-C-like short-range order in the nematic phase well above the S_A-N transition; and (iii) a large tilt-angle variation in the smectic C phase (0-23·5°C) in a small temperature range (4·1°C). The phase changes across the S_A-I transition, and for the first time across S_F-S_A transition, are carried out by volumetric studies. The detailed inferences of these are also presented.     

X-ray studies of the layer thickness in smectic phases

X-ray investigations of nine smectogenic substances exhibiting the smectic A_d, A₁ and crystalline E phases were performed at various temperatures. X-ray patterns yielded the layer thickness d (A_d, A₁ phases) and orthorhombic unit cell parameters (E phase). The layer thickness of the A_d phase in 4'-n-alkyl-4-cyanobiphenyls (nCBs) has different temperature coefficients for shorter (n = 8-10) and longer (n = 12-14) members, which is explained as resulting from two competing effects: a weakening with temperature of the intermolecular association energy that favours an increase in d, and the increasing number of conformers which reduces the molecular length. A small anisotropy of the thermal expansivity in the smectic phases was found by comparing the linear quantity d(T) with the linearized bulk characteristic of the system, V^-3(T), where V = 1/ρ is the specific volume, ρ is the density. Differences between the slopes of the two quantities are less in the case of the A₁ phase of two nDBTs (5-n-alkyl-2-(4'-isothiocyanatophenyl)-1,3-dioxanes). The present X-ray data and recent results of studies of the low frequency relaxation process in these compounds (under atmospheric as well as elevated pressures) give a consistent picture of molecular reorientations around the short axes in the smectic phases.     

Binary mixtures of smectic A1S with abnormal behaviour

Binary mixtures are composed of compounds belonging to the 4'cyanobiphenyl-4-yl 4'-n -alkylbiphenyl-4 carboxylate homologous series and halogenophenyl 4-(trans-4-n-decylcyclohexyl)benzoate (10XPCHB) have been studied. Compounds CBnAB are smectic A₁ for n ≤ 7 and smectic A_d for n ≥ 8; compounds 10XPCHB are smectic A, only. It was found that the S_Ad phase of compounds CBnAB exhibits ideal miscibility with the S_A1 phase of compounds 10XTCHB, and that the S_A1 phases of both compounds show abnormal behaviour. The S_A1 phase of compounds CBnAB is destabilized and the range of the S_A1 phase is enhanced on the side of 10XPCHB. The reasons for this behaviour are discussed.     

The nematic-isotropic two phase region in mixtures of quasi-spherical solutes in alkylcyanobiphenyls: An E.S.R. study using tempone as probe

The transitional behaviour of binary mixtures, each containing a non-mesomorphic quasi-spherical solute at a low mole fraction in a nematogenic solvent, has been investigated by E.S.R. spectroscopy using 4-oxo-2,2,6,6-tetramethyl-4-piperidinyl-1-oxy (tempone) as a spin probe. This approach makes use of the smaller coupling constant obtained for the spin probe in the orientationally ordered nematic phase relative to that obtained in the isotropic phase. The solutes included Et₄C (tetraethylmethane) and R₄Sn (R = C^b2bH₅, n-C_3H7 and nC_b4H₉). The solvents were 4-n-pentyl-4'-cyanobiphenyl (5CB) 4-n-hexyl-4'-cyanobiphenyl (6CB) and 4-n-heptyl-4'-cyanobiphenyl (7CB). This fast approach compares favourably with other studies. In addition it provides the tempone spectral parameter, f, which is a relative measure of the fraction of the nematic phase at different temperatures within the two phase region.     

The influence of double bonds in the terminal chain of 2-ring compounds on the physical properties of S*c mixtures

We present the properties of S*_c mixtures containing new 2-ring 5-n-alkyl-2-(4-n-alkenyloxyphenyl)pyridines and pyrimidines with systematically varying positions and configurations of the double bond Trans configurations at odd positions (counting the number of atoms from the core including the oxygen and the first carbon atom of the double bond) suppress the S_A phase, increase the S*_c tilt angle, Θ, and the spontaneous polarization, P_s, and lead to long switching times τ. Cis configurations at even positions suppress the nematic phase in favour of smectic phases, decrease Θ and P_s, and shorten τ. Other positional configurational combinations strongly reduce the clearing point. Furthermore, our results indicate that the preferred conformation of the alkenyloxy chain consists of alternating cis and trans units.     

Mesomorphic properties of a homologous series of chiral liquid crystals containing the α-chloroester group

The mesomorphic properties of the N*, S*_c and higher ordered smectic phases have been investigated for a homologous series of 4-[(S)-2-chlor-3-methylbutanoyloxy]-4'-(4-n-alkyloxy-benzoyloxy)biphenyls. They have been characterized by optical texture observation, differential scanning calorimetry (DSC), small angle X-ray scattering and electro-optic measurements. The compounds exhibit a strongly twisted cholesteric phase and smectic phases with large spontaneous polarization and tilt angle values. One or two higher ordered, monotropic smectic phases were found which significantly differ in their rotational viscosity.     

Phase transition studies in 9O.6 and 9O.8

The variation of density with temperature across different phases for two homologues of the N(4-n-alkyloxybenzylidene)-4'-n-alkylanilines (9O.6 and 9O.8) exhibiting the S_AS_CS_FS_G phase variant is determined. The influence of pretransitional effects in the fluctuation dominated non-linear region in the vicinity of the isotropic-smectic A transition and the nucleation growth analogy of this transition are discussed.     

Synthesis and characterization of smectic polymesomorphism in higher homologues of nO.m compounds

Some of the higher homologues of the N-(p-n-alkoxybenzylidene)p-n-alkylanilines, n O.m, compounds with n ≧ 8 and m ≧ 5 have been synthesized and the smectic polymesomorphism studied. The transition temperatures were obtained from both thermal microscopy and differential scanning calorimetry. These compounds in the n O.m series exhibit the usual phase sequences, viz. S_AS_CS_BS_G, and S_AS_BS_G apart from S_AS_CS_FS_G by 9O.8 (and some higher n O.m, like 9O.6). These phases were confirmed by miscibility studies with standard materials. The smectic F phase in 9O.8 compound is also confirmed by an X-ray diffraction study.     

High pressure phase studies of some liquid crystalline cyclohexane derivatives by differential thermal analysis

T(p) phase diagrams for the mesomorphic compounds trans-4-n-butylcyclohexane-1-carboxylic acid 4-cyanophenyl ester (D4N), trans4-n-pentylcyclohexane-1-carboxylic acid 4-n-pentylphenyl ester (D55), trans-4,4'-di-n-propyl-1,1-bicyclohexyl-cis-4-carbonitrile (33CCN), trans-4-methoxy-4'-propyl-1,1'-bicyclohexane (3O1CCH) and trans-4-methoxy-4'-n-butyl-1,1'-bicyclohexane (4O1CCH) are presented. The experiments were performed using high pressure microcomputer-assisted differential thermal analysis equipment in the temperature range 300 to 500 K up to a maximum pressure of 8 kbar. Some special high pressure effects for liquid crystals, such as pressure-induced or pressure-limited phases and changes from monotropic to enantiotropic polymorphism were observed. For the correlation of the experimental results, an extension of the Simon equation was used; one of the regression parameters of the clearing curve equation was found to be correlated with the molecular structure of the liquid crystal substances under test.     

Pyridinium salt liquid crystals Effect of mesogen extension and alkyl chain length

The thermotropism of 1-n-alkyl-(4-methyl and 4-tolyl)pyridinium bromides were compared for alkyl chain lengths ranging from n = 12 to 22 carbons. A smectic A mesophase is present in both series for the longer chain compounds, n ≥ 16, with the clearing temperature being similar for both series but increasing rapidly with chain length. The series with the elongated mesogen also possesses an ordered mesophase identified as smectic G. The transition between this mesophase and the S_A or isotropic phase in the 4-tolyl series, and the transition to and from the crystalline phase in both series, are affected relatively little by the alkyl chain length. It seems that the S_A mesophase is governed primarily by the amphiphilic character of the substances, whereas elongation of the ionic head group is responsible for the appearance of a more ordered mesophase at intermediate temperatures.     

Synthesis and transition temperatures of novel fluorinated chiral liquid crystals containing 1,4-tetrafluorophenylene units

To continue the search for novel series of fluorinated ferroelectric liquid crystals, an additional two series of 4-[(S)-2-methylbutoxy]phenyl 4-[(4-n-alkoxy-2,3,5,6-tetrafluorophenyl)ethynyl] benzoates (C) and 4-(n-alkoxy)phenyl 4-[(4-(S)-2'-methylbutoxy-2,3,5,6-tetrafluorophenyl)] benzoates (D) have been synthesized. Polarizing microscopic textural observations and DSC measurements of the phase transitions of these novel compounds showed that compounds C were liquid crystals with a chiral nematic (N) phase and a monotropic chiral smectic C phase (S_c), and compounds D exhibited a chiral nematic (N) phase.     

Novel fluorinated liquid crystals. II. The synthesis and phase transitions of a novel type of ferroelectric liquid crystals containing 1,4-tetrafluorophenylene moiety

4-[(S)-2-Methylbutoxycarbonyl]phenyl 4-[(4-n-alkoxy-2,3,5,6-tetrafluorophenyl)ethynyl]benzoates have been prepared from the starting material 1-pentafluorophenyl-2-trimethylsilylacetylene. Polarizing microscope textural observation and DSC measurements of the phase transitions of these novel compounds showed that they were liquid crystals with chiral smectic C phase (S*_C), smectic A(S_A) and cholesteric (Ch) phases. The effects of the alkoxy chain length on the transition temperatures and enthalpies were also studied.     

Evidence of continuous evolution of smectic A2 from smectic Ad

We present here precise measurements of the layer spacing for two compounds, viz. 4-n-heptyloxyphenyl-4'-(4'-cyanobenzoyloxy)benzoate and 4-n-undecyloxyphenyl-4'-(4'-cyanobenzyloxy)benzoate. Contrary to earlier reports our data do not show any jump in the layer spacing at the expected A_d-A₂ transition temperature, showing thereby that for both compounds A₂ evolves continuously from the A_d phase.     

X-ray investigation of the nematic and reentrant nematic phases of N-[(4-n-octyloxybenzoyloxy)-salicilidene]-4'-cyanoaniline

We have performed an X-ray scattering study of the nematic-smectic A and reentrant nematic-smectic A phase transitions in N-[(4-n-octyloxybenzoyloxy)-salicilidene]-4'-cyanoaniline (OOBOSCA). A diffractometer with a linear position sensitive detector was used. The results show that the smectic phase in OOBOSCA is of the A_d type with an interlayer spacing incommensurate with the molecular length L; d ∽ 1·2L. In the reentrant nematic phase two types of fluctuation modes were found. One of them corresponds to the monolayer wavevector q₁ ∽ 2π/L, and the other is due to the partial bilayer fluctuations with the wavevector q₂ ∽ 0·8q₁. The temperature dependences of the interlayer spacing, X-ray scattering intensity and longitudinal correlation length for both types of layering in the reentrant nematic phase are presented. The change of the fluctuation regime from S_Ad, to S_Cd type with decreasing temperature in the reentrant nematic phase of OOBOSCA was found. The results are discussed on the basis of models with competing order parameters. The influence of alkyl chain flexibility on the stability of a partial bilayer smectic phase is also considered.     

The effect of biasing electric field on the soft mode in the vicinity of the ferroelectric phase transition in liquid crystals

The complex permittivity of a room-temperature ferroelectric liquid crystal 4-n-octyloxy benzoic acid 4'-[(2-methylbutyloxy)carbonyl]phenyl ester, has been measured in the vicinity of the phase transition in the frequency range 40 Hz-300 kHz. In the para-electric phase the contribution ε_s of the soft mode to the permittivity and the soft-mode relaxation frequency f_s satisfy the Curie-Weiss law. Under a biasing field E, the helicoidal structure is unwound, and ε_s and f_s can then be measured even in the ferroelectric phase. On the other hand, the phase transition is smeared under the influence of E. This smearing results in deviations from the Curie-Weiss law for both ε_s and f_s in the vicinity of the transition. On increasing E, the maximum of the permittivity, ε_max, is lowered and shifted to higher temperatures. Both the shift and ε^-1_max are proportional to E^2/3. From experimentally found dependences, some constants in the free energy are determined.     

Dimerization of polar smectics A1 with a terminal cyano group in the matrix of smectics A1 of lower polarity

Binary mixtures have been studied of polar compounds with smectic A₁ phases belonging to the following series: 4-cyanobiphenyl 4-yl 4'-n-alkylbiphenyl-4-carboxylate (CBnAB) and 4-(trans-4-n-decylcyclohexyl) benzoates (10XPCHB) with X = F, NCS, COCH₃. In these systems a strong destablization of the smectic A₁ phase is observed on the side of the CBnAB component and an enhancement of the smectic A₁ phase on the side of 10XPCHB. It is shown that the anomalous behaviour of the mixtures of two A₁ smectics with a similar layer spacing is due to the dimerization of CBnAB in the matrix of 10XPCHB which is of lower polarity.     

High pressure studies of the static permittivity tensor components in the nematic phase of 6CB

The dielectric permittivity tensor components, ε_II and ε_⊥, in the nematic phase of 6CB (4-n-hexyl-4'-cyanobiphenyl) were measured in the pressure range 0.1-130 MPa and the temperature range 12-58°C. The dielectric anisotropy, Δε(p, V, T) = ε_II - ε_⊥, was analysed in isothermal, isobaric and isochoric conditions taking into account the pVT data and the well known Maier and Meier equation. On that basis the nematic order parameter S(p, V, T) was determined. This was used to calculate the parameter Γ relating the interaction potential with the volume (density). Its value Γ = 4.1 agrees very well with other estimates.     

The synthesis and liquid crystalline behaviour of 2-(4-n-alkoxyphenyl)-5-methylpyridines

We have synthesized a new series of polyphenylene compounds with a pyridine ring, 2-(4-n-alkoxyphenyl)-5-methylpyridines (CH₃C₅H₃NC₆H₄OC_iH_2i1) (1a-i; the carbon number, i, of the alkoxy group is 1-9), and studied their phase transitions and mesogenicity using DSC and polarizing microscopy. In the homologous series of 1a-i, no mesomorphic phase appeared for i=1-5 and only a monotropic nematic phase was observed for i=6-9. The mesomorphic potential is relatively weaker for the 1a-i than for the 2a-i and 3a-i homologues, which are pyridine-containing three- and four-ring similar systems. This lowering of the mesogenicity may be due to the lack of a phenyl ring between the pyridine ring and the methyl group in the 1a-i homologues.     

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

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.     

Columnar liquid crystals in oligosaccharide derivatives. II. Two types of discotic columnar liquid-crystalline phase of cellobiose alkanoates

A series of cellobiose octaalkanoates, Cel-II-n (n is the carbon number of the alkyl chain), with n = 7-14 were prepared and their mesogenic properties examined by differential scanning calorimetry, optical polarizing microscopy and X-ray diffraction. All of these compounds form enantiotropic discotic columnar phases, in which the columns are built up by a regular stacking of the cellobiose moieties and are packed in a two dimensional lattice. Homologues with n = 9-14 form the D_ho phase only whilst the compound with n = 7 forms the D_ro phase. The n = 8 compound forms the D_ho phase at higher temperatures and the D_ro phase at lower temperatures. Structural parameters obtained from X-ray diffraction studies are presented for both phases.