Some remarks on the evolution of research into the structures of mesogens and mesophases

Research on mesogens and mesophases began with the surprising observation of a fluid and birefringent phase formed by a pure compound having a calamitic (rod-like) molecule. The structures of the smectic A, nematic and cholesteric phases which emerged after this discovery were elucidated essentially by observations with a polarizing microscope. Smectic polymorphism was also established by microscopic observations. The structures of the different smectic mesophases previously predicted theoretically, was then obtained further type of purposely designed mesophase was the pyramidic type, also exhibiting a rich polymorphism. Research on mesogens and mesophases is a field in continuous expansion. main historical results on the are listed here. The discotic mesophase, and its polymorphism observed. A     

First order transitions to a lyotropic biaxial nematic

The phase diagram of the sodium dodecylsulphate/decanol/water system is studied by²H NMR spectroscopy in the range between the calamitic nematic (N⁺_C) and discotic nematic (N^-_D) phases. In this narrow range a nematic biaxial phase (N_BX) is observed. The phase transitions between the nematic phases are all of first order. The shape of the surfactant aggregates in the nematic phases varies with composition and temperature.     

Phase behaviour of the dioctadecyldimethylammonium bromide-water system

The phase behaviour of the twin-tailed surfactant dioctadecyldimethylammonium bromide with water was studied by DSC, FT-IR, X-ray and polarizing microscope. The phase diagram of DODAB-water system is very similar to that of DODAC-water. The dihydrate is in equilibrium with isotropic solution below 55°C. Above this temperature there is a lamellar liquid crystalline region, in equilibrium with isotropic liquid and solid crystals of DODAB·2H₂O, up to 69°C. From 69 to 86°C, the lamellar mesophase is in equilibrium with ‘waxy’ anhydrous DODAB. From 86 to 116°C and very high DODAB content, there is a very narrow region of existence of inverse hexagonal mesophase, in equilibrium via a narrow biphase region with lamellar mesophase. AtT > 116°C an isotropic liquid appears. There seems to exist two different lamellar mesophases, one of them between 10 and 40 wt.% DODAB and the other between 60 and about 97 wt.% DODAB, with a biphase zone between them.     

First order transitions to a lyotropic biaxial nematic

Abstract

The phase diagram of the sodium dodecylsulphate/decanol/water system is studied by²H NMR spectroscopy in the range between the calamitic nematic (N⁺ _C) and discotic nematic (N^? _D) phases. In this narrow range a nematic biaxial phase (N_BX) is observed. The phase transitions between the nematic phases are all of first order. The shape of the surfactant aggregates in the nematic phases varies with composition and temperature.     

NMR investigation of the dynamics of banana shaped molecules in the isotropic phase: a comparison with calamitic mesogens behaviour

The first translational self-diffusion NMR measurements in the isotropic phase of banana-shaped liquid crystals are reported. In this paper, two banana-shaped mesogens, having a similar molecular structure and showing a nematic phase, have been investigated by means of translational self-diffusion NMR, (2)H NMR spin-spin and (1)H NMR spin-lattice relaxation measurements in the isotropic phase. While (1)H diffusion and (2)H relaxation times reveal a peculiar slow dynamic behaviour of banana-shaped mesogens compared with calamitic mesogens, the (1)H relaxation times seem to be affected by fast dynamics only. The origin of these dynamic features is discussed in terms of overall and internal molecular motions, in the frame of recent speculations concerning the formation of molecular clusters or aggregates in the isotropic phase of banana-shaped liquid crystals.     

Overlapping spheres Xα calculatons of the electron affinities and ionization potentials of ethylene,parabenzoquinone and their perfluoro derivatives

Microscopy and deuterium NMR spectroscopy are employed to demonstrate the existence of a thermodynamically independent nematic amphiphilic mesophase in mixtures of perfluoro-octanoate and water between 37.0 to 87.0% by weight of ²H₂O and 284.0 to 348.3 K at 1 atmosphere pressure. This phase is in equilibrium with an isotropic micellar solution and a smeetic lamellars mesophase to, respectively, high and low temperatures. The lamellar to nematic transition line changes from first to second order at a tricritical point corresponding to 42.5% of ²H₂O and 328.0 K, whilst the nematic to isotropic micellar solution transition is first order at all compositions. The measurements suggest the nematic phase is a solution of disc shaped micelles which orient with their unique axis parallel to the direction of an applied magnetic field.     

The influence of sodium chloride and urea on chromonic liquid crystals formed by CI Acid Red 266

Chromonic liquid crystals are currently receiving renewed interest with particular attention on the Edicol Sunset Yellow (ESY)/water system, which forms columnar nematic and hexagonal phases. CI Acid red 266 is structurally fairly similar to ESY and also forms columnar nematic and hexagonal phases but at much lower concentrations (>1%). In this study, we have examined the influence of sodium chloride and urea on chromonic liquid crystals formed by CI acid red 266. The techniques employed were polarising microscopy, X-ray diffraction and ²H NMR. Sodium chloride moves the concentration at which mesophases form to higher values. Once formed, the mesophases are stable to slightly higher temperatures. Screening of the interstack electrostatic repulsions by added electrolyte appears to be responsible for the changes. Urea can be added in fairly large concentrations (up to 25 wt%) without significant changes in mesophase stability. X-ray diffraction measurements show that there is little change in the aggregate structure with added urea. NMR measurements on urea and water ordering show that urea has much larger order parameters than water. Both order parameters are much smaller than values reported for ESY, but this is simply because of the lower dye concentrations. The larger order parameters for urea appear to arise from some intercalation of urea into the acid red 266 stacks. There is no evidence for changes in ‘water structure’ by the addition of urea.     

Glassiness of thermotropic liquid crystals across the isotropic-nematic transition

The orientational dynamics of thermotropic liquid crystals across the isotropic-nematic phase transition have traditionally been investigated at long times or low frequencies using frequency domain measurements. The situation has now changed significantly with the recent report of a series of interesting transient optical Kerr effect (OKE) experiments that probed orientational relaxation of a number of calamitic liquid crystals (which consist of rod-like molecules) directly in the time domain, over a wide time window ranging from subpicoseconds to tens of microseconds. The most intriguing revelation is that the decay of the OKE signal at short to intermediate times (from a few tens of picoseconds to several hundred nanoseconds) follows multiple temporal power laws. Another remarkable feature that has emerged from these OKE measurements is the similarity in the orientational relaxation behavior between the isotropic phase of calamitic liquid crystals near the isotropic-nematic transition and supercooled molecular liquids, notwithstanding their largely different macroscopic states. In this article, we present an overview of the understanding that has emerged from recent computational and theoretical studies of calamitic liquid crystals across the isotropic-nematic transition. Topics discussed include (a) single-particle as well as collective orientational dynamics at a short-to-intermediate time window, (b) heterogeneous dynamics in orientational degrees of freedom diagnosed by a non-Gaussian parameter, (c) fragility, and (d) temperature-dependent exploration of underlying energy landscapes as calamitic liquid crystals settle into increasingly ordered mesophases upon cooling from the high-temperature isotropic phase. A comparison of our results with those of supercooled molecular liquids reveals an array of analogous features in these two important classes of soft matter systems. We further find that the onset of growth of the orientational order in the parent nematic phase induces translational order, resulting in smectic-like layers in the potential energy minima of calamitic systems if the parent nematic phase is sandwiched between the high-temperature isotropic phase and the low-temperature smectic phase. We discuss implications of this startling observation. We also discuss recent results on the orientational dynamics of discotic liquid crystals that are found to be rather similar to those of calamitic liquid crystals.     

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.     

Temperature dependence of the density of calamitic and discotic nematic lyotropic liquid crystals containing sodium lauryl sulphate/decanol/water

Experimental results for the temperature dependence of density at normal pressure for two compositions of sodium lauryl sulphate/decanol/water solutions, exhibiting either a calamitic or a discotic lyotropic nematic phase at room temperature, are presented. Within the limits of experimental precision (±1 ×10^-5 g cm^-3), the systems show no jump in density at the nematic to isotropic phase transition. Over the studied temperature range, the mean thermal expansion coefficients were also evaluated.     

Pulsed gradient NMR study of anisotropic surfactant diffusion in the caesium perfluoro octanoate/D2O system

We use pulsed field gradient ¹⁹F NMR to measure the diffusion coefficients of surfactant molecules in the isotropic and lamellar phases of the caesium perfluoro octanoate (CsPFO)/D₂O system. An aligned lamellar sample is created by cooling through the nematic phase in the presence of a 1·4 T magnetic field. The director in the lamellar phase does not respond to ordinary field strengths, thus the aligned sample can be rotated clockwise or counterclockwise to place the director at a magic angle, where measurement of diffusion coefficients becomes possible. From a pair of so-obtained coefficients, we derive the principal values of the diffusion tensor corresponding to the directions parallel and perpendicular to the director (D_⊥ and D_⊥). We found D_∥ to be at least 20 times D_∥ a much larger anisotropy than is seen in electrical conductivity and water diffusion in similar systems. These results are compared to electrical conductivity, water and dye diffusion measurements.     

The SmCPA phase in five-ring bent-core compounds derived from 5-methoxyisophthalic acid

The synthesis and mesophase characterization of a homologous series of five-ring bent-core compounds derived from 5-methoxyisophthalic acid are described. Most of the compounds exhibit a polar antiferroelectric smectic C phase. Replacement of the terminal n-alkoxy chains by n-alkyl carboxylate groups, not only destabilizes the formation of mesophases but induces a calamitic mesophase. However, extension of the arms of the bent-core molecule by a phenyl moiety stabilizes the switchable phase. The mesophases were investigated using a combination of polarizing optical microscopy, differential scanning calorimetry, X-ray diffraction and electro-optical methods.     

Long- and short-range order in the mesophases of laterally substituted calamitic mesogens and their radial octapodes

The mesomorphic behavior of a calamitic mesogen (4'-undecyloxybiphenyl-4-yl-4-octyloxy-2-(pent-4-en-1-yloxy)benzoate) and of a supermesogenic octapode formed by the side-on attachment of the mesogen to a octasilsesquioxane central core is studied by X-ray diffraction and polarizing optical microscopy. The calamitic compound is found to have a nematic phase that has biaxial domains (cybotactic clusters) of tilted layers throughout its entire temperature range. Domains of analogous structure are also found in both the nematic and the hexagonal columnar mesophases exhibited by the obctapode compound. The spacing of the layers forming the domains is found to have the same, essentially temperature independent value for the calamitic monomer and for the octapode, in both its mesophases. Comparison with compounds of analogous structure shows that this value is determined by the length of the rigid part of the mesogenic unit. Variation of the latter length is shown to have no effect on the size of the hexagonal lattice of the octapode columnar phase or on the stacking distance within the columns. The presence of the biaxial domains in the nematic phase is discussed in connection with the phase biaxiality that has been observed in structurally related tetrapode compounds and the possibility of field induced macroscopic biaxial nematic order.     

Lyotropic mesomorphism in benzopurpurin 4B-solvent system

The results of studying chromonic mesomorphism in benzopurpurin 4B (BP-4B)-water, BP-4B-water-electrolyte (NaCl or KCl), and BP-4B-water-N,N-dimethylformamide (DMF) or formamide (FA) systems are presented. Mesophases are identified using polarization-optical microscopy and the responses of samples to disturbances induced by magnetic field and mechanical deformation. It is shown that, in water and aqueous electrolyte solutions, at BP-4B concentrations of below 0.5 and 1.5 wt %, respectively, an instable nematic mesophase is formed, which is rapidly transformed into an anisotropic gel. In this case, the formation of the nematic mesophase is preceded by the appearance of tactoids. At some concentrations of organic solvents, nematic mesophases, which are stable for a time period of longer than 2 months, are formed in BP-4B-water-DMF (BP-4B concentrations of 1.0 and 1.5 wt %) and BP-4B-water-FA (BP-4B concentration of 1.0 wt %) systems.     

Anion-Exchange-Driven Disassembly of a SiO(2)/CTAB Composite Mesophase: the Formation of Hollow Mesoporous Silica Spheres

Silica-based surfactant/inorganic composite mesophases have been extremely studied. In this work, we developed a mild method to realize the room-temperature disassembly of a SiO(2)/cetyltrimethylammonium bromide (CTAB) mesophase in a neutral medium. Using KMnO(4) as a typical etching agent, SiO(2)/CTAB mesophase spheres were partially disassembled into normal or rattle-type hollow structures. The disassembly of the SiO(2)/CTAB spheres was supposed to be driven by anion exchange between permanganate and silicate ions. This unique method makes possible the selective etching of a SiO(2)/CTAB mesophase over a SiO(2) phase.     

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.     

Magnetic resonance study on lamellar phases of ammonium perfluorooctanoate

The aggregation properties of ammonium perfluorooctanoate (NH₄-PFO) in concentrated aqueous phases have been investigated by magnetic resonance techniques and have been compared with the aggregation properties in dilute solutions. Magnetic resonance methods indicated that NH₄-PFO—water systems with surfactant concentrations below 45% (w/w) behaved as isotropic purely micellar solutions in the temperature range 285–340 K. For higher concentrations the system exhibited a rather complex structure, having both isotropic and anisotropic components. The nematic nature of the anisotropic fraction was demonstrated by ¹⁹F NMR studies. The ¹⁹F NMR and EPR of nitroxides (TempTMA⁺, 5- and 16-DXSA) inserted as paramagnetic probes into the concentrated NH₄-PFO—water systems allowed us to establish that the lamellar phase could be mechanically oriented between quartz slides. The EPR investigation also gave details concerning the dynamics of both the oriented and non-oriented structures.     

Ionic diffusion and salt dissociation conditions of lithium liquid crystal electrolytes

Salt dissociation conditions and dynamic properties of ionic species in liquid crystal electrolytes of lithium were investigated by a combination of NMR spectra and diffusion coefficient estimations using the pulsed gradient spin-echo NMR techniques. Activation energies of diffusion (Ea) of ionic species changed with the phase transition of the electrolyte. That is, Ea of the nematic phase was lower than that of the isotropic phase. This indicates that the aligned liquid crystal molecules prepared efficient conduction pathways for migration of ionic species. The dissociation degree of the salt was lower compared with those of the conventional electrolyte solutions and polymer gel electrolytes. This is attributed to the low concentration of polar sites, which attract the dissolved salt and promote salt dissociation, on the liquid crystal molecules. Furthermore, motional restriction of the molecules due to high viscosity and molecular oriented configuration in the nematic phase caused inefficient attraction of the sites for the salt. With a decreased dissolved salt concentration of the liquid crystal electrolyte, salt dissociation proceeded, and two diffusion components attributed to the ion and ion pair were detected independently. This means that the exchange rate between the ion and the ion pair is fairly slow once the salt is dissociated in the liquid crystal electrolytes due to the low motility of the medium molecules that initiate salt dissociation.     

Synthesis and characterisation of novel isoxazole-based banana liquid crystals from naturally occurring curcumin

Isoxazole-based bent-core liquid crystals (LCs) derived from naturally occurring curcumin were synthesised and their LC properties were investigated by polarising optical microscopy, differential scanning calorimetry and X-ray diffraction techniques. Five compounds, including a branched alkyl chain derivative, were prepared and characterised. These derivatives exhibit enantiotropic mesophases. While lower homologues display wide-temperature-range nematic phase, a longer-chain derivative 3d shows smectic C phase in addition to the nematic phase. The bent angle in these compounds is in between calamitic LCs and banana LCs. Therefore, the molecules escape from polar order packing observed in typical bent-core LCs. Increasing the length of alkyl chain reduces both melting and isotropic temperatures in the series. However, the compound with branched alkyl chains exhibits significant reduction in the nematic-isotropic temperature only. Detailed XRD experiments confirm the presence of the N phase in the lower homologues and SmC phase in a higher homologue.     

New liquid crystals containing the benzothiazol unit: amides and azo compounds

Two series of calamitic liquid crystals containing a benzothiazole ring within the central core and two different linkage groups (amide and azo) have been prepared and their liquid crystalline properties studied and compared with those of the analogous series of imines. The influence of the linkage group within the central core has been proven to determine the variety of mesomorphism displayed by the compounds. The compounds with imine and azo linkages behave in a similar way and exhibit typical nematic and smectic C mesophases. Compounds incorporating an amide linkage show a poorer mesomorphism and mainly present a smectic C mesophase.