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Lyotropic liquid crystal gels (LLC gels) are versatile materials which combine the anisotropy of a liquid crystal with the mechanical stability of a gel. We succeeded in gelling the rare calamitic nematic NC phase of two different micellar LLC systems with the low molecular weight gelator (LMWG) 3,5-bis-(5-hexylcarbamoyl-pentoxy)-benzoic acid hexyl ester (BHPB-6). The systems of choice are: (1) a binary LLC system with the surfactant N,N-dimethyl-N-ethyl-1-hexadecylammonium bromide (CDEAB) and water; (2) a ternary LLC system with the surfactant N,N,N-trimethyl-N-tetradecylammonium bromide (C14TAB), n-decanol, and water. The obtained gels show optical birefringence and no macroscopic flow. Freeze fracture electron microscopy (FFEM) images show ribbon-like gel fibres that form the gel network and can stack into thicker bundles, while small-angle X-ray scattering (SAXS) confirms the coexistence of the nematic NC phase and the gel network. The growth of the gel network was monitored with time-resolved SAXS measurements. Additionally, significant gel ageing effects were observed in rheology measurements, showing that the gel strengthens with time. With this study, we considerably broaden the pool of available surfactant-based LLC gels and pave a way to macroscopically aligned LLC gels with the goal to apply them as stimuli-responsive actuators and sensors. [ABSTRACT FROM AUTHOR]

We investigate the origins of 'de Vries-like' liquid crystalline behaviour by introducing an ethynyl spacer in the core of the tricarbosilane-terminated 5-phenylpyrimidine mesogens QL16-6 and QL17-6. The rationale for this structural change is based on the assumption that an ethynyl spacer would create more free volume in the core sub-layer and therefore decrease the orientational order parameter S2 in the SmA phase. The tricarbosilane-terminated mesogens WL41-5 and WL42-6 with a 5-(phenylethynyl)pyrimidine core in either a normal or inverted orientation were synthesised, and their mesomorphic and 'de Vries-like' properties characterised using polarised optical microscopy, differential scanning calorimetry, birefringence measurements, small–angle (SAXS) and 2D X-ray scattering. Reduction factors R derived from SAXS and optical tilt angle measurements suggest that neither WL41-5 (R = 0.49) nor WL42-6 (R = 0.80) exhibit 'de Vries-like' properties. The S2(T) profiles show an increase in orientational order with decreasing temperature and a sharp discontinuity at the SmA-SmC transition, which is consistent with 'de Vries-like' behaviour. However, the Leff(T) profiles suggest an increase in interdigitation that reduces the positive effect of increasing S2 in compensating for the molecular tilt. [ABSTRACT FROM AUTHOR]

In de Vries smectic liquid crystals, the transition from the orthogonal smectic A (SmA) to the tilted smectic C (SmC) phase occurs with essentially no decrease in smectic layer thickness. This unusual behaviour is commonly explained assuming a 'hollow-cone' or 'volcano-like' orientational distribution function (ODF) of rod-like molecules in SmA and the transition to SmC being a pure disorder-order transition in the molecular tilt directions. However, even after 20 years of extensive investigations, the experimental confirmation of this ad hoc model is still inconclusive. While optical and electro-optic studies of many de Vries smectics can be readily explained with the hollow-cone model, X-ray diffraction (XRD) studies as well as many polarised Raman spectroscopy (PRS) studies support a broad Maier-Saupe distribution of a sugarloaf-like shape. We review and summarise X-ray, electro-optic and PRS results on the ODFs in the SmA phases of materials claimed to be of the de Vries type and discuss how seemingly contradicting findings can be true at the same time. In molecules where the core is far from collinear with the long molecular axis, the cores may exhibit a volcano ODF while the molecular axes exhibit a sugarloaf ODF. [ABSTRACT FROM AUTHOR]

A series of cyanobiphenyl dimers attached via alkoxy spacers to a central malonate were prepared, and the mesomorphic behaviour was studied by differential scanning calorimetry (DSC), polarised optical microscopy and X-ray diffraction (Wide-angle X-ray scattering and Small-angle X-ray scattering). Depending on spacer lengths and substitution of the malonate, nematic and smectic A mesophases with pronounced odd-even effect were observed. C-2-unsubstituted malonates formed nematic phases for chain lengths C6-C14, while C12 and C14 homologues displayed additional smectic A phases. In contrast, malonates with fluorinated tails at C-2 displayed exclusively smectic A phases. Remarkably, the X-ray diffraction profile of the smectic A phase of the C-2-unsubstituted C12 malonate showed a fundamental (001) and the corresponding third-order (003) diffraction peak, but no (002) reflection. Using Fourier analysis, the diffraction pattern was converted to an electron density profile, which was in good agreement with the proposed packing model of the SmA mesophase based on a horseshow- or hairpin-like conformation of the malonate. [ABSTRACT FROM AUTHOR]

In some liquid crystal (LC) mixtures of bent-core host molecules that form helical nanofilaments (HNFs) and chiral, rod-shaped molecular guests, the spontaneous chirality of the HNFs is not influenced by the guest handedness. In other mixtures, the filaments become homochiral, responding to the handedness of the guest. We show that the important distinction between these two behaviours is the solubility of the guest material in the HNF phase. In our experiments, chiral LC mesogens doped into the HNF phase result in an enantiomeric imbalance and sometimes change the phase sequence on cooling from the isotropic melt. [ABSTRACT FROM PUBLISHER]

Ionic liquid crystals based on congruent ion pairs composed of mesogenic cations and anions of similar shape provide an attractive tool for the tuning of mesophase properties. Here, the effect of the number and symmetry of lipophilic side chains and the type of head group on the phase type and thermal mesophase properties was probed by the synthesis and investigation of two series of novel guanidinium and imidazolium sulphonates and compared with the corresponding iodides. Their mesomorphic properties were examined via differential scanning calorimetry, optical polarising microscopy and X-ray diffraction. While derivatives bearing only one alkoxy chain in either cation or anion with up to three alkoxy chains in total within the ion pairs display smectic A mesophases, hexagonal columnar mesophases were observed for all other compounds with four or five alkoxy chains totally irrespective of the head group. However, with increasing steric bulk, i.e. with a total of six alkoxy chains, the symmetry of the aryl moiety in the anion as well as the type of head group becomes relevant, resulting in hexagonal columnar or plastic phases for guanidinium sulphonates with symmetrical anions, while those with unsymmetrical anions were non-mesomorphic. In contrast, the corresponding imidazolium sulphonates displayed cubic phases for the combinations of symmetrical cation/symmetrical anion and symmetrical cation/unsymmetrical anion. If both ions are unsymmetrically substituted, the imidazolium sulphonate displayed a hexagonal columnar phase. The results further demonstrate the utility of the congruent ion pairs for tailor-made ionic liquid crystals. [ABSTRACT FROM PUBLISHER]

Lyotropic nematic and cholesteric liquid crystalline phases were produced using the racemic amphiphiles, potassiumN-dodecanoyl-DL-alaninate (DL-KDDA) andDL-serinate (DL-KDDS) and theirl-enantiomers, potassiumN-dodecanoyl-L-alaninate (L-KDDA) andL-serinate (l-KDDS), respectively. The different racemic nematic and cholesteric phases were characterised by a polarising light microscope. In order to calculate the helical twisting powers (htp) of the cholesteric phases, their pitches were determined as a function of concentrations of theL-enantiomers. The results showed that theL-KDDA system had a higher helical twisting power than theL-KDDS system. Small-angle X-ray scattering (saxs) techniques were performed for determination of the structural differences between the racemic micelles and the chiral micelles of the racemic and intrinsic cholesteric phases, respectively. Saxs results showed that the intrinsic cholesteric micelles are more compact than their corresponding racemic micelles. These results were interpreted in terms of the different molecular arrangements of the chiral amphiphiles in micelles compared to the amphiphiles in racemic micelles. According to our experimental results and the results on induced cholesteric phases in the literature, we proposed that there must be (1) a crucial distance and (2) a critical micelle size in order to obtain chiral induction, supporting some theoretical studies reported in the literature. In addition, we also showed that chiral induction does not take place completely as was suggested by pairwise interaction or sterical interaction models in the literature, but through anisotropic chiral interactions via distorted micelles for which a crucial distance between the micelles and a critical micelle size are required. [ABSTRACT FROM AUTHOR]

Herein, we report the synthesis and characterisation of liquid crystalline crown ethers bearing central [15]crown-5, unsymmetric [18]crown-6 and [21]crown-7 with lateral o-terphenyl and triphenylene substituents. Comparison with similar derivatives of [12]crown-4, symmetric [18]crown-6 and [24]crown-8 revealed beneficial effects of symmetry reduction on the mesomorphic properties. Decreasing symmetry led to broader phases and melting points at lower temperatures. [ABSTRACT FROM AUTHOR]

A liquid crystalline compound with the azo group in the molecular core and three lactic acid units in the chiral chain (n = 3) was synthesised and its mesomorphic properties established. Spontaneous polarisation and tilt angle were determined in the ferroelectric and antiferroelectric smectic C phases. Dielectric spectroscopy in the frequency range of 1 Hz-10 MHz was performed within the temperature range of smectic phases showing the characteristic modes in each phase. Small-angle X-ray diffraction was performed and temperature dependences of layer spacing value calculated. Comparison with previously studied compounds with one (n = 1) and two lactate units (n = 2) is presented to establish the effect of lactate unit number on the liquid crystalline properties. [ABSTRACT FROM AUTHOR]

In this paper, a series of crown ether-based liquid crystals was synthesised. The effect of different crown ether ring sizes, terminal groups and complexed salts on the mesomorphic properties was investigated. The first example of [12]crown-4 as the central core of a discotic liquid crystal is described. Columnar hexagonal phases were found for the [12]crown-4-ethers carrying o-terphenyl (1) and triphenylene (2) groups. The [24]crown-8 ethers showed columnar hexagonal phases when substituted with o-terphenyl groups (7) while no mesophases could be detected in the case of the triphenylene substituted derivatives 8. It was found that an increase in the size of the macrocycle leads to a decrease in the clearing points and phase stabilities. Depending on the size of the crown ether, uptake of suitable cations can lead to drastic increases in the clearing temperatures and phase stabilities due to structural rearrangements or ion pair formation, as deduced from 1H and 13C NMR spectroscopy. [ABSTRACT FROM AUTHOR]

Novel lactic acid derivatives containing an azo group in their molecular core have been synthesised and their mesomorphic properties established. Compounds with a short aliphatic non-chiral chain exhibited the SmA* phase and ferroelectric (FE) SmC* phase. The monotropic antiferroelectric (AF) phase was found in the homologues with a longer terminal chain. Spontaneous polarisation and tilt angle were measured for the FE and AF phases. Dielectric spectroscopy in the frequency range 1 Hz-10 MHz was carried out and dielectric properties established within the temperature range of the smectic phases. Two high frequency modes were detected in the AF phase. Small-angle X-ray measurements were conducted, and the temperature dependence of layer spacing values is established and discussed. [ABSTRACT FROM AUTHOR]

There is a great interest in smectic materials that show no layer shrinkage (NLS) in the transition from smectic A to smectic C. Such materials are often discussed in terms of “de Vries materials” or “de Vries behavior” after A. de Vries, who proposed different mechanisms for this NLS behavior, involving a significant tilt β of the individual molecules in the smectic A phase. According to the original proposition of de Vries, the molecules are already tilted in this kind of smectic A phase, with a large constant tilt and the same tilt direction in each layer but random tilt direction between different layers. Despite the individual molecular tilt the smectic A phase remains uniaxial and the transition to the biaxial smectic C state is seen as a global ordering in the tilt directions. The model thus ad hoc predicts that there is zero layer shrinkage at the A - C transition. We refer to this model as the “hollow cone distribution”. As later pointed out by de Vries there are, however, other possible models for describing a tilt disorder (thermodynamically unavoidable) in the A phase. Nevertheless, the hollow cone has been a widely accepted model in the literature and is repeatedly referred to in discussing de Vries behavior or even taken as a basis for theories describing it. We discuss different smectic A orientational distribution functions that could be related to de Vries behavior or de Vries transitions. We find that two opposite models have comparable predictive power but only one gives a consistent picture together with existing data. Our conclusion is that the smectic A - smectic C transition can have a continuously changing character from a “pure tilt” to a “pure de Vries”, and we illustrate the orientational distribution functions in the A and C phases for these two limiting cases. We find that de Vries behavior is not related to any exotic distribution of hollow cone or similar kind in the A phase, but instead to an unusual combination of low nematic order and high smectic order in the de Vries smectic A. As the technical interest in such materials is considerable, a directed effort toward the synthesis of new optimized materials would be important. [ABSTRACT FROM AUTHOR]

Novel calamitic guanidinium salts with p-alkoxybiphenyl or p-alkoxyphenyl core unit (7, 11, 12) have been synthesised, utilising the corresponding nitro compounds as synthetic intermediates. Differential scanning calorimetry (DSC), polarising optical microscopy (POM) and temperature-dependent X-ray diffraction studies reveal smectic A (SmA) mesophases for all series. Whereas the p-alkoxybiphenyl guanidinum chlorides 7 display SmA phases with a minimum chain lengths of C8 and broad mesophase width from 80°C (for C8 derivative 7b) up to 180°C (for C16 derivative 7g), the corresponding p-alkoxyphenyl guanidinium chlorides 11 display much smaller mesophase width from 4°C (for C10 derivative 11c) up to 72°C (for C16 derivative 11e). For the series 12 a large influence of the anion on the clearing point is observed, with clearing points ranging from 209°C for the guanidinium chloride 7f down to 127°C for guanidinium hexafluorophosphate 12d. [ABSTRACT FROM AUTHOR]

A new series of materials with a chiral fragment derived from lactic acid and a methoxy group as lateral substituent in different positions of the molecular core was synthesised and investigated. Derivatives with ester or ether linkages of the non-chiral chain were also studied. Depending on the molecular structure, cholesteric, twist grain boundary smectic A (TGBA*), chiral smectic A (SmA*) or chiral smectic C (SmC*) phases were detected. In derivatives with the ester linkage and a methoxy group at the nearest and the next nearest phenyl ring to the non-chiral chain these phases completely disappear. On the other hand, a methoxy group on the phenyl ring close to the chiral chain provides a compound with low layer shrinkage at the SmA*-SmC* phase transition (“de Vries” behaviour). The temperature dependence of the spontaneous polarisation, the tilt angle, the layer spacing as well as the complex permittivity were studied and the results discussed in terms of molecular structure. [ABSTRACT FROM AUTHOR]

A series of 2-(4-n-alkylphenyl)indenes (3) with different alkyl substituents (CH3 to C10H21) were synthesized and systematically characterized using differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction compared with 2-phenylindene (3a). Depending on the alkyl chain length, highly ordered crystal-smectic E mesophases were observed and confirmed by X-ray diffraction for the derivatives 3h-3k with heptyl to decyl chains (n = 6-9). For 3f with a pentyl side chain (n = 4), an X-ray crystal structure analysis was carried out. [ABSTRACT FROM AUTHOR]

Using a discrete model for the synclinic SmC* and the anticlinic SmCa* phases we give a theoretical explanation for the fact that the helix twisting sense reverses at a transition between these phases (direct transition or via the so-called chiral smectic C ‘subphases’) and we derive an explicit expression for the helical pitch in the SmCa* phase. As the theory shows and as we also demonstrate experimentally, the reversal is of a different nature from helix inversions within a single phase, where the inversion is always coupled to a pitch divergence. At a clinicity change the common behaviour is instead pitch-shortening on approaching the phase transition and the associated helix twisting sense reversal. The phenomenon may be put to use in smart mixing in order to control the helix pitch, either for achieving long pitch for surface-stabilized ferroelectric and antiferroelectric liquid crystal displays; or a very short pitch, in the case of devices utilizing the deformed helix mode. [ABSTRACT FROM AUTHOR]

We report the synthesis and liquid crystalline properties of novel ester-substituted tetraphenylenes obtained from octamethoxytetraphenylene by demethylation and esterification. The target compounds display focal-conic textures typical for columnar mesophases, which are either rectangular or hexagonal columnar in nature, depending on the alkyl chain length. [ABSTRACT FROM AUTHOR]

A new semi-fluorinated chiral smectic liquid crystal, W504, is investigated by electro-optic, dielectric and X-ray scattering experiments. It exhibits a huge dielectric soft mode response, strong electroclinic effect and a birefringence which increases considerably with the director tilt angle ?; typical characteristics of a SmA*–SmC* transition following the de Vries asymmetric diffuse cone (ADC) model in which the non-zero director tilt in SmC* arises through an ordering of tilting directions rather than an actual increase in average molecule tilt mol >. In W504 a small increase in mol > of about 4° is however detected in the SmC* phase. Although the increase in molecule inclination is much less than the increase in director tilt ?, saturating close to 30°, it leads to a shrinkage of the smectic layers by about 1 Å, a result of the large initial molecule tilt in the SmA* phase, mol > SmA* ˜30°. The tilting transition in W504 is thus mainly an ADC model disorder–order transition, but it also has a component of a structural transition. The semi-fluorinated molecular structure of W504 leads to a very weak electron density modulation along the layer normal, giving a vanishing form factor in bulk samples which exhibit no (0 0 1) X-ray scattering peak. In thin films the (0 0 1) peak is however observed, indicating that the electron density modulation is enhanced by the breaking of the head–tail symmetry of the liquid crystal phase at the LC–air interface. [ABSTRACT FROM AUTHOR]

A phenomenological approach to the description of the electrolyte effect on the nematic–isotropic phase transition in lyotropic liquid crystals is proposed. The influence of the electrolyte is discussed by varying the coupling between the concentration variables and the orientational order parameter. The analysis shows that the discontinuity in the first order nematic–isotropic phase transition as measured by increases as a function of the weight fraction of the electrolyte. Here T NI is the first order nematic–isotropic phase transition temperature and is the extrapolated supercooling limit. The electrolyte dependence of the Cotton–Mouton coefficient and the non‐linear dielectric effect in the isotropic phase above the nematic–isotropic phase transition are calculated. The theoretical predictions are found to be in good agreement with experimental results. [ABSTRACT FROM AUTHOR]

By mixing a bistereogenic antiferroelectric liquid crystal (AFLC) compound, exhibiting only the SmQ and SmCa mesophases, with the achiral N-SmC liquid crystal HOAB we could induce all three AFLC SmC-type subphases, SmCα, SmCβ and SmCγ. This seems to be in contradiction with two recent postulations regarding the subphase stability, one of which suggests that the subphases appear as a result of strong chiral interactions, the other that these phases require high smectic order something one would generally not expect in mixtures. We have studied the helical pitch, optical tilt angle, spontaneous polarization and the x-ray diffraction due to the smectic layering, as a function of mixing ratio in order to better understand the relation between phase sequence and mixture composition. The smectic layer spacing shows a strongly non-linear behavior suggesting that the basic structure of the pure AFLC substance is retained up to a HOAB content of about 75%. [ABSTRACT FROM AUTHOR]

We report the synthesis and liquid crystalline properties of novel mesogenic octaalkyloxytetraphenylenes. Starting from 4-bromoveratrol, the saddle-shaped target tetraphenylenes were obtained in five steps. Compounds with shorter C7-C12 alkyl chain lengths displayed enantiotropic hexagonal columnar mesophases. For the decyloxy derivative a lattice constant d =27.4 Å was determined by X-ray diffraction. The compounds with longer C13-C16 alkyl chains exhibited enantiotropic mesophases, which are most probably smectic in nature. X-ray diffraction of the R =C 14 H 29 derivative indicated a phase transition within the smectic mesophases. [ABSTRACT FROM AUTHOR]

We have investigated the orthoconic antiferroelectric liquid crystal mixture W107 by means of optical, X-ray and calorimetry measurements in order to assess the origin of the unusally high tilt angle between the optic axis and the smectic layer normal in this material. The optical birefringence increases strongly below the transition to the tilted phases, showing that the onset of tilt is coupled with a considerable increase in orientational order. The layer spacing in the smectic A* (SmA*) phase is notably smaller than the extended length of the molecules constituting the mixture, and the shrinkage in smectic C* (SmC*) and smectic C a * (SmC a *) is much less than the optical tilt angle would predict. These observations indicate that the tilting transition in W107 to a large extent follows the asymmetric de Vries diffuse cone model. The molecules are on average considerably tilted with respect to the layer normal already in the SmA* phase but the tilting directions are there randomly distributed, giving the phase its uniaxial characteristics. At the transition to the SmC* phase, the distribution is biased such that the molecular tilt already present in SmA* now gives a contribution to the macroscopic tilt angle. In addition, there is a certain increase of the average tilt angle, leading to a slightly smaller layer thickness in the tilted phases. Analysis of the wide angle scattering data show that the molecular tilt in SmC a * is about 20° larger than in SmA*. The large optical tilt (45°) in the SmC a * phase thus results from a combination of an increased average molecule tilt and a biasing of tilt direction fluctuations. [ABSTRACT FROM AUTHOR]

The substance MHPOBC is the oldest and still most important reference antiferroelectric liquid crystal (AFLC). There is still considerable controversy concerning the correct phase designations for this material and, in particular, about the presence or absence of SmC * in its phase sequence. By means of dielectric spectroscopy and polarizing microscopy, we show that whereas the pure compound lacks the SmC * phase, this phase rapidly replaces the SmC * β subphase through the reduced purity resulting from temperature-induced chemical degradation which is hard to avoid under standard experimental conditions. X-ray investigations furthermore show that this change in phase sequence is coupled to a decrease in translational order. This explains the large variations in the reported phase sequence and electro-optic behaviour of MHPOBC, in particular concerning the SmC * β phase which has been said to exhibit ferro-, ferri- as well as antiferroelectric properties. It is likely that the sensitivity of the AFLC phase sequence to sample purity is a general property of AFLC materials. We discuss the importance of optical and chemical purity as well as tilt and spontaneous polarization for the observed phase sequence and propose that one of the key features determining the existence of the different tilted structures is the antagonism between orientational (nematic) and translational (smectic) order. The decreased smectic order (increased layer interdigitation) imposed by chemical impurities promotes the synclinic SmC * phase at the cost of the AFLC phases SmC * α , SmC * β , SmC * γ and SmC * a . We also propose that the SmA * phase in FLC and AFLC materials may actually have a somewhat different character and, depending on its microstructure, some of the tilted phases can be expected to appear or not to appear in the phase sequence. AFLC materials exhibiting a direct SmA * -SmC * a transition are found to be typical 'de Vries smectics', with very... [ABSTRACT FROM AUTHOR]

Some new calamitic chiral mesogens (2,5-diphenyl-1,3,4-thiadiazoles, 2,5-diphenylpyrimidines and a biphenylyl benzoate) incorporating the 1-alkylpropynyl moiety have been synthesized as enantiomerically enriched materials (ee c. 87%) and/or as racemates. Their liquid crystalline properties were studied by polarizing microscopy, differential scanning calorimetry and electro-optical investigation. Thereby it was found that most of the new compounds exhibit smectic C phases. The spontaneous polarization (Ps) of the optically active materials was measured to be around 10 nCcm-2. [ABSTRACT FROM AUTHOR]