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.     

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.     

Sulphur containing mesogens. The mesophasic behaviour of di(4-alkyloxybenzoates) of 4,4'-dimercaptobiphenyl

A homologous series of di(4-alkyloxybenzoates) of 4,4'-dimercaptobiphenyl: CH₃(CH₂)_n-1O-C₆H₄-COS-C₆H₄-C₆H₄-SOC-C₆H₄-O(CH₂)_n-1CH₃,n=1-7, has been synthesized and the thermotropic liquid-crystalline behaviour investigated. All compounds exhibit enantiotropic mesomorphism over a remarkable temperature range. While the mesophase thermal stability is moderately higher than that found for the corresponding oxygenated analogues, the smectic stability is definitely lower. In fact, all the compounds are nematic but smectic mesomorphism (S_C) is observed for n = 7. Compounds with n = 6 or 7 exhibit enantiotropic highly ordered smectic (or disordered crystal) phases, probably S_G in type.     

Heterocyclic benzoxazole-based liquid crystals

The synthesis, characterization, and mesomorphic properties of a new type of heteronuclear compounds 1a-c and a Pd complex 1d derived from benzoxazole as the core group are reported. These compounds were prepared by the ring closure reaction of 4-alkoxybenzoic acid 4-[(4-alkoxy-2-hydroxyphenylimino)methyl]phenyl esters 6 in the presence of lead(IV) acetate. All the compounds were characterized by ¹H and ¹³C NMR spectroscopies and elemental analysis. The phase behaviour of these mesogenic compounds was characterized and studied by differential scanning calorimetry and polarizing optical microscopy. All the compounds 1a exhibited nematic (N) and/or smectic C (SmC) phases, as expected for rod-like molecules; however, the compounds 1b and 1c exhibited crystal phases. For those compounds 1a having shorter carbon chains (n = 1, 3, 4) nematic phases were observed, whereas for compounds having longer carbon chains (n = 6, 7, 8, 10, 12, 14) smectic C behaviour was also observed at lower temperatures. The greater aspect ratio (l/d) of compounds 1a compared with 1b and 1c was found to be required for the observation of liquid crystallinity. The fluorescent properties of these compounds were also examined. All λ_max peaks of the absorption and photoluminescence spectra of compounds 1a-1c occurred at c. 316-322 nm and 371-382 nm, respectively. The quantum yields of some compounds were relatively low, and also slightly solvent-dependent.     

Liquid-crystalline behaviour of some bis(4-alkyloxyphenyl) thiazolo [5,4-d] dithiazoles

The preparation of liquid-crystalline 2,5-bis(4-alkyloxyphenyl) thiazolo [5,4-d] dithiazoles (ATT_n), in which the alkyl group is C_nH_{2n + 1} (where n = 1 to 10, 12), has been described. Mesomorphic properties and phase transitions as determined by polarizing hot stage microscopy and differential scanning calorimetry are discussed as a function of the number of carbon atoms in the alkyloxy chain. The exhibition of tilted smectic phases (smectic C and smectic I) by these compounds is an interesting feature since there is no significant central dipole moment transverse to these molecules.     

Synthesis and thermal properties of mesomorphic 1,1'-bis[ω-(4'-cyano-4-biphenyloxy)alkyl] ferrocenes

A new series of 1,1'-disubstituted ferrocene compounds of the type [(η⁵-C₅H₄(CH₂)_nOC₆H₄C₆H₄CN]₂Fe (3a-d, n = 5, 6, 8, 11) incorporating a variable length alkyloxy cyanobiphenyl unit has been prepared and their mesomorphic properties have been investigated. Compounds 3b, c and d exhibit a thermotropic smectic C phase and 3c also exhibits a monotropic smectic A phase over a fairly wide range near ambient temperature.     

Oscillations in thin nematic layers

In the present paper a thin nematic liquid crystal layer between two identical boundary surfaces (solid walls or free surfaces in the case of a freely suspended film) is considered. In a mean field approximation it is shown that the interference between the boundary surface-induced smectic density waves results in oscillations of the free energy of the nematic layer and disjoining pressure acting on the boundary surfaces. Theoretical dependence of disjoining pressure on the nematic layer thickness is in qualitative agreement with experiment. Also we have considered a thin film of polar nematic in which in addition to an ordinary monolayer smectic A phase (S_A1) with the layer thickness d equal to the molecular length l the partial bilayer smectic A phase (S_Ad) occurs. It is shown that the variation of the distance between the boundary surfaces can result in the oscillatory S_A1-A_Ad phase transitions in this nematic film     

Molecular motion and phase transition in perovskite-type (CH3)nNH4−nSnCl3 (n=1–4) studied by proton NMR spin–lattice relaxation

Powder X-ray diffraction, ¹¹⁹Sn NMR spectra, and ¹H NMR spin–lattice relaxation times, T₁, were measured for (CH₃)_nNH_4−nSnCl₃ (n=1–4). From the Rietveld analysis, it is shown that all four compounds crystallize into deformed perovskite-type structures at room temperature. The temperature dependence of ¹H T₁ was analyzed in terms of the CH₃ reorientation and other motions of the whole cation. Except for the phase transition in CH₃NH₃SnCl₃, which is from monoclinic to rhombohedral at 331 K, ¹H T₁ was continuously changed at other phase transitions in this compound as well as in the n=2–4 compounds, suggesting that the transitions are not caused by the change of the motional state of the cation but by an instability of the [SnCl₃]_nⁿ⁻ perovskite lattice.     

Synthesis and thermal properties of dimeric alkoxy-substituted tolans

Four homologous series of dimeric tolans of the general formula RC₆H₄C≏C₆H₄O(CH₂)_m OC₆H₄C'CC₆H₄R (m'6-10; R'H, OC₆H₁₃, OC₁₀H₂₁ and OC₁₄H₂₉), denoted further as TOmOT or nOTOmOTOn, according to the number of aliphatic carbon atoms, have been synthesized. Dimers with terminal chains exhibited liquid crystalline behaviour. Crystal-crystal transitions were also observed. Resulting from the optical, thermal and miscibility studies, the following mesophases have been identified: nematic, smectics A and B, and the tilted smectics C and (probably) F or I. In the 6OTOmOTO6 series, a phase with a strong tendency to self-alignment occurred between the nematic and smectic A phases. This phase resembled the nematic in its viscoelastic properties, but also showed focal-conic textures. A transition between this 'intermediate phase' and the nematic was detected only from microscopic observations. On the contrary, the 'intermediate phase'-smectic A transition was also detected by DSC (δH ∼ 1kJ mol^-1). Both tilted (S_c and S_F/I) and non-tilted (S_A and S_B) smectics were observed in the 10OTOmOTO10 series, while only tilted smectic phases were identified in the dimers with longer terminal substituents (14OTOmOTO14). Double melting behaviour was found in 14OTO8OTO14 and 14OTO10OTO14. An alternation of the transition temperatures and enthalpies with the odd-even alternation of the lengths of bridging groups was clearly observed. A correlation between total enthalpies of transition and solubilities of the dimeric tolans is stated.     

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.     

Investigation on lanthanide binuclear complexes of 1,5-bis-(1′-phenyl-3′-methyl-5′-pyrazolone-4′)-1,5-pentanedione and 2,2′-bipyridine

The coordination of 1,5-bis-(1′-phenyl-3′-methyl-5′-pyrazolone-4′)-1,5-pentanedione (BPMPPD) and 2,2′-bipyridine (bipy) with lanthanide ions in water-alcohol solution has been studied. Binuclear complexes of the types : Ln₂(BPMPPD)₃(bipy)₂·nH₂O (n = 2 for Y, n = 4 for Eu, Gd, Dy, Ho, Er, Tm and Yb); Ln₂(BPMPPD)₃bipy·nH₂O (n = 10 for La, n = 3 for Pr, Nd, Sm and Tb) were formed. The compounds were characterized by elemental analysis, molar conductance, IR, UV, ¹H NMR spectroscopy, thermogravimetric analysis and fluorescence spectra.     

Optical microscopy, DSC and X-ray diffraction studies in binary mixtures of 4-pentyloxy-4'-cyanobiphenyl with three 4,4'-di(alkoxy)azoxybenzenes

A large number of binary mixtures of 4-pentyloxy-4'-cyanobiphenyl (5OCB) and 4,4'-di(alkoxy)azoxybenzenes (nOAB) with n = 5, 6 and 7 have been studied by optical microscopy, DSC and X-ray diffraction methods. Over a wide concentration range the smectic A (SmA) phase is induced and the nematic (N) phase of the parent compounds is absent. Instead of the tilted smectic C phase of 7OAB an orthogonal SmA phase is observed when only 12% of the host molecules are replaced by 5OCB molecules. Moreover, in some mixtures the thermal stability of the induced SmA phase is found to be more than 1.6 times the stability of the mesophses in the pure compounds. The N-isotropic or Sm-I transition temperatures slowly increases with increasing concentrations, reaching a maximum at x _5OCB = 0.50 and then falling quite rapidly. In all the mixtures the enthalpy changes at the N-I transitions follow the simple additivity rule. In no mixture, except mixture C2, could the SmA-N transition be detected by DSC, although in all the mixtures the ratio T _NA/T _NI is found to be more than 0.95, which is in contradiction to McMillan's theory. Average intermolecular distances are found to have a minimum value near the equimolar concentration. From the concentration dependence of the smectic layer spacings it also appears that in all the mixtures the smectic A_d phase evolves from the smectic A₁ phase with increasing concentrations.     

A nematic phase created in mixtures of polar smectics The effect of smectic layer properties

Phase diagrams of binary mixtures composed of compounds with the NCS terminal group (n-DBT, n-PBT, n-TPB (smectic A₁) or n-BT (smectic E₁)) and n-OCB, n-CB (smectics A_d) are presented. It is shown that the width of the nematic gap that separates the A₁ or E₁ phase region from the smectic A_d phase is related to the interaction energy of the molecules in the smectic layers and to the difference in the smectic layer spacings.     

X-ray study of the nematic and smectic A phases of the cyano-substituted pyridines

We report an X-ray study of lamellar ordering in the nematic and smectic A phases of a homologous series of polar liquid crystals, the 2-(4-alkylphenyl)-5-cyanopyridines (nCP). Experiments were carried out using a diffractometer with a linear position sensitive detector. In the nematic and smectic A phases of the nCP and their mixtures with non-polar 4-n-butyl-4'-methoxyazoxybenzene two types of layering were found. One corresponds to the fluctuations of the smectic density wave with a monolayer wavevector q₁, and the other is due to the partial bilayer fluctuations with the incommensurate wavevector q₂ ≠ q₁/2. The temperature dependences of the X-ray scattering intensity and the longitudinal correlation length for both types of layering in the nematic phase are presented. The critical behaviour in the vicinity of the smectic A-nematic phase transition occurs for a fluctuation mode, either q₁ or q₂, depending on the position on the liquid crystal phase diagram. The influence of the molecular structure of cyano-substituted pyridines on the formation of layered structures of different types is also discussed.     

Thermotropic liquid crystalline comb-like polymers with polyacrylamide main chain. (2) Influence of the nature of the substituents of the biphenyl mesogenic core

Comb-like polymers with polyacrylamide main chains and three types of lipophilic biphenyl side chains have been synthesized and their thermotropic behaviour has been determined. All the polymers exhibit two smectic mesophases as a function of temperature, but the nature of the smectic mesophases is governed by the nature of the substituent R of the biphenyl core. For R = H, the polymers exhibit a double layer, ordered, tilted smectic S_i2 and a double layer, disordered, tilted smectic S_c2. For R = CN, the polymers exhibit a double layer, disordered, tilted smectic S_c2 and a double layer, disordered, perpendicular smectic S_A2. For R = O-CH₂-CH(CH₃)-C₂H₅, the polymers exhibit a double layer, ordered, tilted smectic S_f2 and a double layer, disordered, tilted smectic S_c2, these two structures being chiral when the substituent R is chiral. Comparison of the thermotropic behaviour of the polyacrylamide polymers with that of polymers with the same mesogenic cores but different main chains shows the high smectogenic power of the polyacrylamide skeleton.     

A comparison of mesogenic properties of p-carborane-1,12-dicarbaldehyde schiff's bases with their terephthaldehyde analogues

A homologous series of carborane-containing Schiff's bases 1A[n] (n = 1-10) was prepared and compared with the analogous series 1B[n] derived from terephthaldehyde. An exponential fit of the T _NI values for both series yielded a quantitative assessment of the effect of ring structure on mesophase stability. This includes the T _NI value for n→∞ (86°C for 1A[n] and 209°C for 1B[n]) and steepness of descent (0.135 for 1A[n] and 0.095 for 1B[n]). The difference in behaviour of the two series was attributed, largely, to conformational properties of the central rings A and B. Electronic interactions between the central rings and the π-substituents were investigated by UV spectroscopy and by quantum-mechanical calculations. The effect of replacement of O with CH₂ in the terminal chain of 1[n] on the namatic phase stability was assessed for n = 5-7.     

Effect of molecular structure on the phase behaviour of some liquid crystalline compounds and their mixtures XII. Binary mixtures of homologues of unsymmetrical 1,4-phenylene bis (4-substituted benzoates)

Twentyfour liquid crystalline esters of the type 4-(n-C_nH_2n+1O)C₆H₄COOC₆H₄OOCC₆H₄-X-4 have been investigated for their phase behaviour. These compounds constitute six homologous series that differ from each other by the substituent X. The latter varies between CH₃O, CH₃, Cl, CN, NO₂, and n-C_nH_2n+1O, and the number (n) of carbons varies, within a homologous series, between 6, 8, 14, and 16. All possible binary mixtures made from any two homologues were prepared and characterized for their mesophase behaviour by differential scanning calorimetry and polarizing optical microscopy.     

Phase behaviour of the thermotropic cubic mesogen 1,2-bis(4-n-decyloxybenzoyl)hydrazine under pressure

The phase transition behaviour of an optically isotropic, thermotropic cubic mesogen 1,2-bis(4-n-decyloxybenzoyl)hydrazine, BABH(10), was investigated under pressures up to 300 MPa using a high pressure differential thermal analyser, a wide angle X-ray diffractometer and a polarizing optical microscope (POM) equipped with a high pressure optical cell. The reversible change in structure and optical texture between the cubic (Cub) and smectic C (SmC) phases was associated with a change from a spot-like X-ray pattern and dark field for the Cub phase to the Debye-Sherrer ring pattern and sand-like texture for the SmC phase under both isobaric and isothermal conditions. The Cub phase was found to disappear at pressures above about 11 MPa. The phase transition sequence, low temperature crystal (Cr₃)-intermediate temperature crystal (Cr₂)-high temperature crystal (Cr₁)-Cub-SmC-isotropic liquid (I) observed at atmospheric pressure, is maintained in the low pressure region below 10 MPa. The transition sequence changes to Cr₃-Cr₂-(Cr₁)-SmC-I in the high pressure region. Since the Cub-SmC transition line determined by POM has a negative slope (dT/dP) in the T-P phase diagram, a triple point is estimated approximately at 10-11 MPa, and 143-145°C for the SmC, Cub and Cr₁ phases, giving the upper limit of pressure for the observation of the cubic phase.     

Phase behaviour of three homologues of the discotic hexa-n-alkoxyanthraquinones under pressure

The phase transition behaviour of three homologous discotic mesogens, the hexa-n-alkoxyanthraquinones HOAQ(n), n indicating the number of carbon atoms in the alkoxy group, was investigated under hydrostatic pressures up to 500 MPa using a high pressure differential thermal analyser. The T vs. P phase diagrams of HOAQ(6), HOAQ(8) and HOAQ(9) were constructed for solution- (Cr₀) and melt-crystallized (Cr₁) samples of the compounds. HOAQ(6) shows the reversible Cr₀-rectangular columnar phase (Col_r)-hexagonal columnar phase (Col_h)-isotropic liquid (I) phase sequence at atmospheric pressure. The stable Col_r phase of HOAQ(6) has a decreased temperature range with increasing pressure and then the Col_r phase disappears under pressures above about 350 MPa; instead the Cr₀-Col_h-I phase sequence is exhibited. For HOAQ(8), the solution-grown sample exhibits the stable Cr₀-Col_h-I phase sequence at atmospheric pressure. Applying pressure to the solution-grown sample induces the formation of the stable Col_r phase in the pressure region between 10 and 350 MPa, leading to the Cr₀-Col_r-Col_h-I phase sequence. The pressure-induced Col_r phase disappears under higher pressures. The melt-cooled sample of HOAQ(8) shows the formation of the metastable crystal (Cr₁), unknown mesophase (X) and Col_r phases at lower temperatures under atmospheric pressure, and exhibits the reversible Cr₁-X-Col_r-Col_h-I phase sequence on subsequent thermal cycles. The metastable phase sequence was observed under pressures up to 100 MPa, but the phase transitions were too small to be detected under higher pressures. In HOAQ(9) the stable Cr₀-Col_h-I phase sequence is observed at all pressures, while the melt-cooled sample shows the metastable Cr₁-Col_r-Col_h-I phase sequence under pressures up to 300 MPa. The metastable Col_r phase disappears under higher pressures.     

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.