The mesomorphic anomaly of 4-[2-(4-alkoxy-2,3,5,6-tetrafluorophenyl)ethynyl] phenyl trans-4-pentylcyclohexyl-1-carboxylates

Four homologous series of 4-[2-[4-alkoxy-2,3,5,6-tetrafluorophenyl)ethynyl] phenyl trans-4-alkylcyclohexyl-1-carboxylates have been prepared. Their liquid crystalline behaviour was investigated by optical polarizing microscopy and DSC. Series A, B and C exhibit the nematic phase. The phase transition behaviour of series D is anomalous. The compounds of series D with a short alkoxy chain exhibit enantiotropic smectic A and nematic phases, while those with a long alkoxy chain exhibit only the nematic phase.     

The mesomorphic anomaly of 4-[2-(4-alkoxy-2,3,5,6-tetrafluorophenyl)ethynyl] phenyl trans-4-pentylcyclohexyl-1-carboxylates

Four homologous series of 4-[2-[4-alkoxy-2,3,5,6-tetrafluorophenyl)ethynyl] phenyl trans-4-alkylcyclohexyl-1-carboxylates have been prepared. Their liquid crystalline behaviour was investigated by optical polarizing microscopy and DSC. Series A, B and C exhibit the nematic phase. The phase transition behaviour of series D is anomalous. The compounds of series D with a short alkoxy chain exhibit enantiotropic smectic A and nematic phases, while those with a long alkoxy chain exhibit only the nematic phase.     

The homologous series of some new six-ring double-swallow-tailed compounds

Recently we reported three homologous six-ring double-swallow-tailed compounds. For one homologue we observed the unusual phase sequence re-entrant smectic C-D_ob-smectic C-nematic. For this reason, results for a more complete homologous series are now presented. It was found that the phase behaviour can be compared with some series of biforked compounds. The lower members of the series exhibit nematic and smectic C phases, whereas the long-chain homologues form columnar phases. For three members of the series with intermediate lengths of the terminal chains, lamellar (S_c) and columnar (D_ob) phases occur for the same substance.     

Chiral liquid crystalline m-nitrotolans and tolans: synthesis and mesomorphic properties

Two homologous series, 4'-(4-n-alkoxybenzoyloxy)-4-substituted 3-nitrotolans (Ia-d) and 4'-(4-n-alkoxybenzoyloxy)-4-substituted tolans (IIa-c), with substituents (S)-2-methyl-1-butyl and n-alkyl, were synthesized by Sonogashira's coupling. Their mesomorphic behaviour is reported. The thermal stability of the series II is higher than that of series I. Series I melting points and clearing points are lower than those of series II. None of the chiral tolans or m-nitrotolans have an enantiotropic smectic C phase. When the chiral chains are changed to n-alkyl groups in compounds Ia,b and IIa, an enantiotropic smectic C phase is seen. All compounds have a nematic or cholesteric phase, and two homologues of series II present a monotropic smectic C phase with mosaic texture. The mesophases were characterized using optical polarized light microscopy and differential scanning calorimetry.     

Synthesis and phase behaviour of a homologous series of polymethacrylate-based side-chain liquid crystal polymers

The homologous series of side chain liquid crystal polymers, the poly[ω-(4-methoxyazobenzene-4′-oxy)alkyl methacrylate]s, has been prepared in which the length of the flexible alkyl spacer has been varied from 3 to 11 methylene units. All the polymers exhibit liquid crystalline behaviour. The propyl and butyl members show exclusively nematic behaviour. The pentyl, hexyl, octyl and decyl members show a nematic and a smectic A phase while the heptyl, nonyl and undecyl homologues exhibit only a smectic A phase. The smectic A phase has been studied using X-ray diffraction and assigned as a smectic A₁ phase in which the side chains are fully overlapped and the backbones are confined to lie between the smectic layers. For the nonyl member an incommensurate smectic phase is observed. The dependence of the transition temperatures on the length of the flexible spacer is understood in terms of the average shapes of the side chains.     

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.     

Nematic and smectic mesophases in a new series of Cu(II) organometallic complexes

The synthesis and the phase behaviour of a homologous series of copper, bis[N-[[4-[4-(alkoxy)benzoyloxy],2-hydroxyphenyl]methylene]-methanamino] complexes is reported. They all exhibit thermotropic mesomorphism. The thermal stability range of the mesophase decreases slightly with increasing length of the alkoxy terminals. With the onset of smectic mesomorphism, for alkoxy groups containing ten carbon atoms, the stability interval of the nematic phase decreases progressively so that the compound containing 14 carbon atoms in the alkoxy terminal chains exhibits only smectic mesomorphism. Optical texture analysis suggests the smectic C nature of the phase in all cases. The enthalpies for the liquid crystal-isotropic transition have been measured and they are comparatively low. Remarkably low values have also been measured for the melting enthalpies of the smectogenic members of the series. These are associated with solid phase polymorphism which is discussed briefly.     

U-Shaped dimeric liquid crystals derived from phthalic acid

Details of the transitional properties of four homologous series of U-shaped liquid crystal materials, the benzene-1,2-di-(4-carboxyalkoxybenzylidene-4-n-alkylanilines), are presented. The spacers incorporate 3 to 6 methylene units, whilst terminal aliphatic chain lengths are varied from 1 to 12 units. Members of the two homologous series with an odd number of methylene units in the spacer form nematic and smectic phases as a function of terminal chain length. Materials with an even number of methylene units in the spacer are purely smectogenic, and in both series the first two homologues form only smectic B phases. For all four series the higher homologues show the phase sequence SF/I-SC-SA-I. X-ray diffraction studies have shown that these smectic phases are composed of molecules arranged in bilayers.     

Three ring dioxanes as dopants enhancing the stability of the smectic C phase

Searching for compounds which could be useful as modifiers of smectic C mixtures, we have synthesized four homologous series of three ring dioxanes, 2BBD, 5BBD, 2CBD, and 5CBD. Their phase transition temperatures and enthalpies were measured and their liquid crystal phases identified. Compounds belonging to series n-BBD form smectic B_cr phases for shorter alkyl chains, and smectic B_cr and A phases, for longer chains. Compounds belonging to the n-CBD series exhibit the smectic A phase, but those with longer alkyl chains have exclusively smectic B phases and those with short tails have other low temperature, highly ordered smectic phases. The compounds were added to smectic C mixture and it was found that some can be useful as dopants. Compounds with longer alkyl tails in the molecule are more suitable for this purpose; the type of ring in the core is less important.     

Synthesis and mesomorphic properties of semi-perfluorinated chain liquid crystals

Three homologous series of 4-(n-polyfluoroalkoxycarbonyl)phenyl 4-[(4-n-alkoxyphenyl)ethynyl] benzoates have been synthesized from 1,1,3-trihydroperfluoropropanol, 1,1,5-trihydroperfluoropentanol and 1,1,7-trihydroperfluoroheptanol. Polarizing microscopic textural observations and DSC measurements of the phase transitions of these compounds show that most of them are thermotropic liquid crystals with smectic A and very broad smectic C phases; furthermore, several show very narrow monotropic SmB phases. The effect of the terminal polyfluoroalkoxy and alkoxy groups on the mesomorphic behaviour is also discussed.     

Three ring dioxanes as dopants enhancing the stability of the smectic C phase

Abstract

Searching for compounds which could be useful as modifiers of smectic C mixtures, we have synthesized four homologous series of three ring dioxanes, 2BBD, 5BBD, 2CBD, and 5CBD. Their phase transition temperatures and enthalpies were measured and their liquid crystal phases identified. Compounds belonging to series n-BBD form smectic B_cr phases for shorter alkyl chains, and smectic B_cr and A phases, for longer chains. Compounds belonging to the n-CBD series exhibit the smectic A phase, but those with longer alkyl chains have exclusively smectic B phases and those with short tails have other low temperature, highly ordered smectic phases. The compounds were added to smectic C mixture and it was found that some can be useful as dopants. Compounds with longer alkyl tails in the molecule are more suitable for this purpose; the type of ring in the core is less important.     

Chiral ordering in the nematic and an optically isotropic mesophase of bent-core mesogens with a halogen substituent at the central core

Two new homologous series of bent-core compounds have been synthesized. Their mesophase behaviour has been investigated by polarizing microscopy, differential scanning calorimetry, X-ray diffraction, NMR spectroscopy, and by dielectric and electro-optical measurements. It was found that, with one exception, all the chlorine-substituted compounds form a nematic phase and an optically isotropic 'banana phase'. The latter phase shows spontaneously chiral domains of opposite handedness. This phase may be considered as a type of smectic blue phase. The mesophase behaviour of the homologous bromine-substituted compounds is more complicated. Depending on the chain length, B₆, columnar, nematic or the isotropic 'banana phase' occur.     

Chiral ordering in the nematic and an optically isotropic mesophase of bent-core mesogens with a halogen substituent at the central core

Two new homologous series of bent-core compounds have been synthesized. Their mesophase behaviour has been investigated by polarizing microscopy, differential scanning calorimetry, X-ray diffraction, NMR spectroscopy, and by dielectric and electro-optical measurements. It was found that, with one exception, all the chlorine-substituted compounds form a nematic phase and an optically isotropic ‘banana phase’. The latter phase shows spontaneously chiral domains of opposite handedness. This phase may be considered as a type of smectic blue phase. The mesophase behaviour of the homologous bromine-substituted compounds is more complicated. Depending on the chain length, B₆, columnar, nematic or the isotropic ‘banana phase’ occur.     

Preorganised effects of a tetramesogenic supermolecule on supramolecular assembly in the liquid crystalline phases

After preparing a homologous series of tetrameric mesogenic compounds in which two U-shaped molecules were connected via a rigid benzene derivative or a flexible alkyl chain, we investigated their phase transition behaviour using optical microscopy, differential scanning calorimetry and X-ray diffraction analysis. The compounds possessing an alkyl spacer as the central group exhibited nematic and smectic A phases just as the corresponding U-shaped molecule did. The compound possessing a 1,2-benzene unit as the connecting group showed nematic and smectic A phases, although the compound possessing a 1,3-benzene unit exhibited only an anticlinic smectic C phase. Structure–property relations of the liquid crystalline tetramers are interpreted in terms of preorganised effects of the four mesogenic units.     

Bent-core V-shaped mesogens consisting of salicylaldimine mesogenic segments: synthesis and characterization of mesomorphic behaviour

A series of bent-core V-shaped mesogens consisting of salicylaldimine mesogenic segments have been synthesized and their mesomorphic behaviour characterized. In an attempt to understand structure-property relationships, the lengths of the terminal alkoxy chains have been varied from C₂ to C₁₂, C₁₆ and C₁₈, resulting in 13 new bent-core V-shaped molecules. The thermal behaviour of these new compounds has been investigated by optical microscopy, calorimetry and X-ray diffraction studies. In general the compounds show conventional mesophases similar to those shown by calamitic LCs. The materials exhibit good thermal stability, even though their melting and clearing transition temperatures are high as a result of the presence of intramolecular hydrogen bonding between the H-atom of the hydroxyl group and the N-atom of the imine functionality. The phase appearing in the first member of the series with ethoxy chains is a nematic, while the C₃ to C₆ derivatives exhibit a smectic A phase as well as a nematic phase. The higher homologues, C₇ to C₁₂, C₁₆ and C₁₈, show only the smectic A phase. X-ray studies reveal that the SmA phase has a partially bilayer (interdigitated) structure. Remarkably, in some cases, the smectic A phase supercools well below room temperature. It is apparent from our studies that increasing the length of the alkoxy chains promotes smectic behaviour, in agreement with the general observation made for such bent-core molecules.     

Structural assignment and molecular order of three-ring mesogen by 13C NMR spectroscopy in mesophase

A homologous series of rod-like molecules with three phenyl rings in the core and terminal alkoxy chains are synthesised from mesogenic two-ring aldehyde by coupling with non-mesogenic 4-alkoxy anilines. The mesophase properties are evaluated with hot-stage optical polarising microscopy and differential scanning calorimetry, and accordingly, all the molecules exhibited enantiotropic nematic and smectic C phases along with monotropic low-temperature smectic phases. For a representative homologue, the existence of smectic C phase is further confirmed by noticing a sharp reflection at small angle region in powder X-ray diffraction which varies with change in temperature. The main focus of the investigation, however, is the clear demonstration of chemical shift assignment of static ¹³C NMR of a representative three-phenyl ring mesogen in smectic C phase. In this novel approach, the static ¹³C NMR spectral data of synthetic mesogenic intermediate namely two-ring aldehyde are utilised for the chemical shift assignment of three-ring mesogens. Further, the orientational order parameter of two-ring aldehyde in smectic A and three-ring mesogen in smectic C phase is carried out by measuring the ¹³C-¹H dipolar couplings by 2D separated local field spectroscopy.     

High speed parallel synthesis of banana-shaped molecules and phase transition behaviour of 4-bromo-substituted derivatives

Novel derivative series of the well known bent-shaped P-n-O-PIMB liquid crystal mesogens, referred to as '4Br-P-n-O-PIMB', '4Cl-P-n-O-PIMB' and '5Cl-P-n-O-PIMB', having halogen atoms substituted on the phenyl ring in the central core, were synthesized by solution phase parallel synthesis based on a combinatorial approach. The mesomorphic behaviour and physical properties of all the new compounds were studied by means of optical microscopy, differential scanning calorimetry, X-ray and circular dichroism spectroscopy. We found interesting transitional behaviour for the 4Br-P-n-O-PIMB homologous series. The homologues with alkyl tails having carbon numbers of n=3-10, 12, 14 exhibit rather complicated mesomorphic behaviour, which is strongly sensitive to n. The chiral fluid smectic B2 phase with SmC_AP_A structure and unidentified smectic Bx phase were observed in the homologues with n=9, 10, 12, 14 and n=3-5, respectively. Interestingly, every member exhibits frustrated and/or helical ordered phases at low temperatures, designated as X1, X2, and X3 phases, which result from a spontaneous escape from a macroscopic polarization. The mesomorphic behaviour and mesophase structures differ remarkably from those of the parent P-n-O-PIMB homologues, suggesting that substitution of the halogen atoms at the central core essentially creates a particular interaction between molecules.     

A detailed study of hydrogen bonded ferroelectric mesogens formed between alkyl and alkyloxy benzoic acids with carbamyl glutamic acid

A new ferroelectric homologous series of hydrogen-bonded ferroelectric liquid crystals is designed and synthesised with 14 compounds comprising two homologous series. The hydrogen bond is formed between dicarboxylic acid, viz. Carbamyl glutamic acid (CGA) with p-n-alkyl/alkyloxy benzoic acids (BA/BAO) and is confirmed by Fourier Transform Infrared Spectroscopy (FTIR) and Nuclear Magnetic Resonance (NMR) studies. These two series referred as the CGA+nBAO and the CGA+nBA yields 14 mesogenic homologues and the mesogenic nature is detected by optical textures through polarising microscope which is confirmed through Differential Scanning Calorimetry (DSC). CGA+nBAO series exhibit cholesteric, smectic X*, smectic C* and smectic G* phases while CGA+nBA exhibits cholesteric and smectic G*phases. The enthalpy values of the corresponding temperatures are elucidated. Odd–even effect is evinced at smectic C* to smectic G* phase transition temperatures of CGA+nBAO series. The order of the individual phase transition and thermal stability factor of the phases is also calculated. Optical tilt angle in smectic C* phase is obtained by optical extinction method. Dielectric relaxation and their corresponding frequency shift observed in different ferroelectric phases are measured and a dielectric molecular modelling is presented. Crystallisation kinetic study of smectic G* phase in CGA+nBAO is computed. An interesting phenomenon – ‘Parachromatism’ – is elaborated.     

Odd-even effects in the phase transition behaviour of novel U-shaped liquid crystals

A homologous series of U-shaped dimeric liquid crystals in which two mesogenic groups are connected via catechol has been prepared and the effects of terminal alkyl chains, alkyl spacers and core structures on the transition properties investigated by means of optical microscopy and differential scanning calorimetry. The phase sequence exhibits a pronounced odd-even effect as the length and parity of the spacers is varied, in which the even members favour the nematic and smectic C phases, whereas the odd members favour the nematic and smectic A phases. We discuss the transition behaviour of the U-shaped compounds in terms of molecular shape.     

Structure of the B4 liquid crystal phase near a glass surface

The B4 liquid crystal phase of bent-core molecules, a smectic phase of helical nanofilaments, is one of the most complex hierarchical self-assemblies in soft materials. We describe the layer topology of the B4 phase of mesogens in the P-n-OPIMB homologous series near the liquid crystal/glass interface. Freeze-fracture transmission electron microscopy reveals that the twisted layer structure of the bulk is suppressed, the layers instead forming a structure with periodic layer undulations, with the topography depending on the distance from the glass. The surface layer structure is modeled as parabolic focal conic arrays generated by equidistant parabolas whose foci are defect lines along the glass surface. Nucleation and growth of toric focal conics near the glass substrate is also observed. Although the growth of twisted nanofilaments, the usual manifestation of structural chirality in the B4 phase, is suppressed near the surface, the smectic layers are intrinsically chiral, and the helical filaments that form on top of them grow with specific handedness.