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Ionic liquid crystals (ILCs) are soft matter materials with broad liquid crystalline phases and intrinsic electric conductivity. They typically consist of a rod-shaped mesogenic ion and a smaller spherical counter-ion. Their mesomorphic properties can be easily tuned by exchanging the counter ion. ILCs show a strong tendency to form smectic A phases due to the segregation of ionic and the non-ionic molecular segments. Nematic phases are therefore extremely rare in ILCs and the question of why nematic phases are so exceptional in existing ILCs, and how nematic ILCs might be obtained in the future is of vital interest for both the fundamental understanding and the potential applications of ILCs. Here, we present the result of a simulation study, which highlights the crucial role of the location of the ionic charge on the rod-like mesogenic ions in the phase behaviour of ILCs. We find that shifting the charge from the ends towards the centre of the mesogenic ion destabilizes the liquid crystalline state and induces a change from smectic A to nematic phases., (© 2022 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)

We report the observation of the smectic A F , a liquid crystal phase of the ferroelectric nematic realm. The smectic A F is a phase of small polar, rod-shaped molecules that form two-dimensional fluid layers spaced by approximately the mean molecular length. The phase is uniaxial, with the molecular director, the local average long-axis orientation, normal to the layer planes, and ferroelectric, with a spontaneous electric polarization parallel to the director. Polarization measurements indicate almost complete polar ordering of the ∼10 Debye longitudinal molecular dipoles, and hysteretic polarization reversal with a coercive field ∼2 × 10 5 V / m is observed. The SmA F phase appears upon cooling in two binary mixtures of partially fluorinated mesogens: 2N/DIO, exhibiting a nematic (N)-smectic Z A (SmZ A )-ferroelectric nematic (N F )-SmA F phase sequence, and 7N/DIO, exhibiting an N-SmZ A -SmA F phase sequence. The latter presents an opportunity to study a transition between two smectic phases having orthogonal systems of layers.

Exfoliated platelets of graphene oxide (GO) can be considered as polydisperse 2D colloids that form nematic colloidal liquid crystal phases in aqueous suspension even at very low concentrations thanks to their extremely high aspect ratios. However, with the rapidly emerging scientific interest in these GO-based liquid crystals, it became clear that the precise analysis and control of the GO sheet size distribution is essential, both for their scientific understanding and for potential applications, e.g. , in optoelectronic devices, nanocomposites, or catalysis. In this work, we show that the mean effective (hydrodynamic) GO platelet width can be determined from the translational diffusion coefficient with depolarized dynamic light scattering by using a model for circular, infinitely thin disks. We further studied the phase separation process of biphasic isotropic-nematic GO dispersions and developed a simple fractionation protocol, which can be used to prepare relatively monodisperse fractions of GO sheets with widths ranging from 2.0-12.4 μm. Overall, we expect that the combined application of these relatively simple fractionation and analysis methods will advance the fabrication of well-defined and size-selected GO-based systems.

Two series of flavylium triflates carrying alkoxy side chains in the A-ring (benzo unit of chromylium salt) and thioethers in the B ring (phenyl unit) (O n -Fla-S m ) as well as thioethers at both A and B ring (S n -Fla-S m ) were synthesized in order to understand the effect of thioether functionalization on their self-assembly and electronic properties. Concentration-dependent and diffusion ordered (DOSY) NMR experiments of O 1 -iV-Fla-S 3 indicate the formation of columnar H-aggregates in solution with antiparallel intracolumnar stacking of the AC unit (chromylium) of the flavylium triflate, in agreement with the solid state structure of O 1 -V-Fla-S 1 . Thioether substitution on the B ring changes the linear optical properties in solution, whereas it has no effect on the A ring. According to differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction bulk self-assembly of these ionic liquid crystals (ILCs) depends on the total number of side chains, yielding SmA and Lam Col phases for ILCs with 2-3 chains and Col ro , Col h phases for ILCs with 3-6 chains. Thus, we demonstrated that thioethers are a useful design tool for ILCs with tailored properties., (© 2022 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)

Ionic liquid crystals (ILCs), that is, ionic liquids exhibiting mesomorphism, liquid crystalline phases, and anisotropic properties, have received intense attention in the past years. Among others, this is due to their special properties arising from the combination of properties stemming from ionic liquids and from liquid crystalline arrangements. Besides interesting fundamental aspects, ILCs have been claimed to have tremendous application potential that again arises from the combination of properties and architectures that are not accessible otherwise, or at least not accessible easily by other strategies. The current review highlights recent developments in ILC research, starting with some key fundamental aspects. Further subjects covered include the synthesis and variations of modern ILCs, including the specific tuning of their mesomorphic behavior. The review concludes with reflections on some applications that may be within reach for ILCs and finally highlights a few key challenges that must be overcome prior and during true commercialization of ILCs., (© 2021 The Authors. ChemPlusChem published by Wiley-VCH GmbH.)

Mesoporous silica materials (MSMs) produced by true liquid crystal templating (TLCT) are often considered as direct inverted replicas of the initial lyotropic liquid crystal (LLC) phase. However, the predictive design of tailor-made MSMs requires the full knowledge of the TLCT process, which is still incomplete. Here, we tackle this issue by monitoring the structural evolution during the templating process by small-angle X-ray scattering, showing that after the addition of the silica source the reaction mixture is first isotropic and then an intermediary liquid crystal phase appears, which is the key to the success of the templating process, namely the formation of ordered MSMs. We analyze the structure and the formation dynamics of this intermediary phase and present a simple theoretical model, which allows us to connect the structural parameters of the initial LLC and the MSM. These results provide an enhanced understanding of the TLCT process and are an important step toward the predictable synthesis of new MSMs in the future.

Recent studies have shown that lyotropic nematic liquid crystals (LLCs) are exceptional in their viscoelastic behavior. In particular, LLCs display a remarkable softness to twist deformations, which may lead to chiral director configurations under achiral confinement despite the absence of intrinsic chirality. The twisted escaped radial (TER) and the twisted polar (TP) are the two representative reflection symmetry breaking director configurations in the case of cylindrical confinement with homeotropic anchoring. We demonstrate how such reflection symmetry breaking of micellar LLCs under cylindrical confinement is affected by intrinsic chirality, introduced by the addition of a chiral dopant. Similarities and differences between the effects of intrinsic chirality on the defect-free TER configuration, and on the TP configuration incorporating two half-unit twist disclination lines, are discussed. In the TP case, topological constraints facilitate stable heterochiral systems even in the presence of a small amount of chiral dopant, with unusual regions of rapidly reversing handedness between homochiral domains. At moderate dopant concentrations, the TP structure becomes homochiral. At high dopant concentrations, for which the induced cholesteric pitch is much smaller than the diameter of the capillary, the cholesteric fingerprint structure develops.

Lyotropic liquid crystal (LLC) gels are a new class of liquid crystal (LC) networks that combine the anisotropy of micellar LLCs with the mechanical stability of a gel. However, so far, only micellar LLC gels with lamellar and hexagonal structures have been obtained by the addition of gelators to LLCs. Here, the first examples of lyotropic nematic gels are presented. The key to obtain these nematic gels is the use of gelators that have a non-amphiphilic molecular structure and thus leave the size and shape of the micellar aggregates essentially unchanged. By adding these gelators to lyotropic nematic phases, an easy and reproducible way to obtain large amounts of lyotropic nematic gels is established. These nematic gels preserve the long-range orientational order and optical birefringence of a lyotropic nematic phase but have the mechanical stability of a gel. LLC nematic gels are promising new materials for elastic and anisotropic hydrogels to be applied as water-based stimuli-responsive actuators and sensors., (© 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

In this work we present a systematic study on the microstructure of soft materials which combine the anisotropy of lyotropic liquid crystals with the mechanical stability of a physical gel. Systematic small-angle neutron (SANS) and X-ray (SAXS) scattering experiments were successfully used to characterize the lyotropic lamellar phase (L α ) of the system D 2 O -n-decanol - SDS which was gelled by two low molecular weight organogelators, 1,3:2,4-dibenzylidene-d-sorbitol (DBS) and 12-hydroxyoctadecanoic acid (12-HOA). Surprisingly, a pronounced shoulder appeared in the scattering curves of the lamellar phase gelled with 12-HOA, whereas the curves of the DBS-gelled L α phase remained almost unchanged compared to the ones of the gelator-free L α phase. The appearance of this additional shoulder strongly indicates the formation of a synergistic structure, which neither exists in the gelator-free L α phase nor in the isotropic binary gel. By comparing the thicknesses of the 12-HOA (25-30 nm) and DBS (4-8 nm) gel fibers with the lamellar repeat distance (7.5 nm), we suggest that the synergistic structure originates from the minimization of the elastic free energy of the lamellar phase. In the case of 12-HOA, where the fiber diameter is significantly larger than the lamellar repeat distance, energetically unfavored layer ends can be prevented, when the layers cylindrically enclose the gel fibers. Interestingly, such structures mimic similar schemes found in neural cells, where axons are surrounded by lamellar myelin sheets.

We present a systematical investigation of gelled lyotropic liquid crystals (LLCs). This new class of soft materials combines the anisotropy of LLCs with the mechanical stability of a physical gel. The studied LLC system consists of sodium dodecyl sulfate as a surfactant, n -decanol as a cosurfactant, and water as a solvent. At room temperature, four liquid crystalline phases (lamellar L α , nematic N d and N c , and hexagonal H 1 ) are formed depending on the composition. We were successful in gelling the lyotropic lamellar phase with the low-molecular-weight organogelator 12-hydroxyoctadecanoic acid (12-HOA). The obtained gelled lamellar phase shows optical birefringence, elastic response, and no macroscopic flow. However, we were not able to obtain gels with hexagonal or nematic structure. These findings can be explained twofold. When gelling the hexagonal phase, the long-range hexagonal order was destroyed and an isotropic gel was formed. The reason might be the incompatibility between the gel fiber network and the two-dimensional long-range translational order of the cylindrical micelles in the hexagonal phase. Otherwise, the lyotropic nematic phase was transformed into an anisotropic gel with the lamellar structure during gelation. Evidently, the addition of the gelator 12-HOA to the lyotropic system considerably widens the lamellar regime because the integration of the surface-active 12-HOA gelator molecules into the nematic micelles flattens out the micelle curvature. We further investigated the successfully gelated L α phase to examine the impacts of the gel network and the remaining monomeric gelator on both the structure and properties of the gelled lamellar phase. Small-angle X-ray scattering results showed an arrested lamellar layer spacing in the gelled state, which indicates a higher translational order for the gelled lamellar phases in comparison with their gelator-free counterparts.

X-ray diffraction (XRD) is one of the most important methods to assess the long-range translational order in smectic A (SmA) liquid crystals. Nevertheless, the knowledge about the influence of the molecular electron density distribution (MEDD) on the XRD pattern is rather limited because it is not possible to vary the orientational order, the translational order and the MEDD independently in an experiment. We here present a systematic simulation study in which we examine this effect and show that the MEDD indeed has a major impact on the general appearance of the XRD pattern. More specifically, we find that the smectic layer peaks and the intensity ratios thereof strongly depend on the width of the MEDD. The classic approach by Leadbetter et al. to determine the smectic translational order parameter ∑ from XRD intensities works if the MEDD is quite narrow. In all other cases the influence of the MEDD has to be taken into account., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A series of tetraguanidinium tetraphenylethene (TPE) arylsulfonates with different chain lengths was prepared via ionic self-assembly of tetraguanidinium TPE chloride and the respective methyl arylsulfonates. Liquid crystalline properties were studied by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction. Tetraguanidinium TPE arylsulfonates with chain lengths of C 8 -C 12 displayed hexagonal columnar mesophases over a broad temperature range, while derivatives with longer chains showed oblique columnar phases. In solution all compounds displayed aggregation-induced emission behaviour. Temperature-dependent luminescence spectra of the bulk phase of the tetraguanidinium TPE arylsulfonate with C 14 side chains revealed a strong luminescence both in the solid state and the oblique columnar mesophase. The emission behaviour was rationalized by a unique combination of restriction of intramolecular rotation of the TPE core, Coulomb interaction between the guanidinium cations and π-π interactions of the anionic arylsulfonate moieties., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The mesogens QL32-6, QL33-6 and QL-34-6 contain 5-phenylpyrimidine cores and terminal nanosegregating carbosilane end groups of different lengths and are known to exhibit 'de Vries-type' properties of varying strength. We report a systematic study of the influence of the nanosegregating sublayer on the dynamics and rotational viscosities of the collective modes in the smectic A* (SmA*) and smectic C* (SmC*) phase using dielectric spectroscopy. It was found that the dynamics of the Goldstone mode corresponding to phase angle fluctuations are almost not affected while the relaxation time and rotational viscosity of the soft mode are influenced by the degree of nanosegregation. In other words, the nanosegregating sublayer does not influence the dynamics of ferroelectric switching in the SmC* phase, but is critical in inducing 'de Vries-type' properties., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The electro-optic Kerr effect in simple dipolar fluids such as nitrobenzene has been widely applied in electro-optical phase modulators and light shutters. In 2005, the discovery of the large Kerr effect in liquid-crystalline blue phases (Y. Hisakado et al., Adv. Mater. 2005, 17, 96-98.) gave new directions to the search for advanced Kerr effect materials. Even though the Kerr effect is present in all transparent and optically isotropic media, it is well known that the effect can be anomalously large in complex fluids, namely in the isotropic phase of liquid crystals or in polyelectrolyte solutions. Herein, it is shown that the Kerr effect in the isotropic phase of ionic liquid crystals combines the effective counterion polarization mechanism found in polyelectrolytes and the unique pretransitional growth of the Kerr constant found in the isotropic phase of nematic liquid crystals. Maximum Kerr constants in the order of several 10 -11  m V -2 (ten times higher than the Kerr constant of the toxic nitrobenzene and less temperature sensitive than Kerr constants of nematic liquid crystals) make ionic liquid crystals attractive as new class of functional materials in low-speed Kerr effect applications., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

To probe the influence of electrostatic interactions on the mesomorphic self-assembly and phase behaviour of hybrid liquid crystals a series of crown ether/tyrosine hybrid systems was prepared by Steglich esterification of alkyl N-(tert-butoxycarbonyl)-l-tyrosinates with 4-carboxybenzo[15]crown-5 and 4-carboxybenzo[18]crown-6. The obtained derivatives allowed further manipulations at the NH functional group and complexation of the crown ether unit with NaI to give neutral or charged hybrid materials. All compounds were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and X-ray diffraction (XRD) measurements. Neither the variation of the N-protecting group, introduction of charge at the N-terminus nor anion exchange (Cl vs. I) resulted in mesomorphism. In contrast, N-Boc-protected and unprotected hybrids formed rectangular columnar (Col r ) mesophases with phase widths up to 35 K. NaI complexation switched these neutral thermotropic derivatives into ionic liquid crystals (ILCs) and induced a change of mesophase type from Col r to smectic A (SmA). A comparison of experimentally obtained layer distances and theoretically calculated molecular lengths indicated bilayer SmA formation with interdigitated alkyl chains. Packing models for both mesophase types are proposed and discussed with respect to stabilizing interactions.

Recently, the emergence of spontaneous reflection-symmetry-broken configurations in achiral chromonic liquid crystals confined in cylindrical capillaries with homeotropic anchoring at the cylinder walls was reported, namely, the so-called twisted-escaped radial (TER) and twisted planar polar (TPP) configurations. This new example of spontaneous reflection symmetry breaking in liquid crystals was attributed to the twist elastic modulus, which is known to be unusually small in comparison to the splay and bend moduli in the case of chromonic liquid crystals. We now report the experimental observation of reflection symmetry breaking in cylindrical capillaries in the case of a classical, achiral, and nonchromonic lyotropic liquid crystal forming a nematic phase of disklike micelles orienting homeotropically at the capillary walls. We observed the same chiral TER configuration, as well as a nonplanar twisted polar (TP) configuration. The TP configuration is characterized by two half-unit so-called twist disclinations, where the director twist around the line defects drives the formation of a double helix of the disclinations along the axis of the capillary. Additionally, there is a transverse twist between the two disclination lines with the same handedness as the axial twist. Similarities with and differences from the case of chromonic liquid crystals are discussed; in particular, we examine the conditions under which spontaneous reflection symmetry breaking occurs in the nonchromonic system. It seems that the chiral TER configuration can be stabilized by the presence of point defects.

Structural variants of the 'de Vries-like' mesogen 5-[4-(12,12,14,14,16,16-hexamethyl-12,14,16-trisilaheptadecyloxy)phenyl]-2-hexyloxypyrimidine (QL16-6), including two isomers with branched iso-tricarbosilane end-groups, were synthesized and their mesomorphic and 'de Vries-like' properties were characterized by polarized optical microscopy, differential scanning calorimetry, small angle and 2D X-ray scattering techniques. A comparative analysis of isomers with linear and branched tricarbosilane end-groups shows that they exhibit comparable mesomorphic and 'de Vries-like' properties. Furthermore, the difference in effective molecular length L eff between the linear and branched isomers in the SmA and SmC phases (ca. 4-5 Å), which was derived from 2D X-ray scattering experiments, suggests that the linear tricarbosilane end-group is hemispherical in shape on the time-average, as predicted by a DFT conformational analysis at the B3LYP/6-31G* level.

In ionic liquid crystals, the orthogonal smectic A phase is the most common phase whereas the tilted smectic C phase is rather rare. We present a new study with five novel ionic liquid crystals exhibiting both a smectic A as well as the rare smectic C phase. Two of them have a phenylpyrimidine core whereas the other three are imidazolium azobenzenes. Their phase sequences and tilt angles were studied by polarizing microscopy and their temperature-dependent layer spacing as well as their translational and orientational order parameters were studied by X-ray diffraction. The X-ray tilt angles derived from X-ray studies of the layer contraction and the optically measured tilt angles of the five ionic liquid crystals were compared to obtain their de Vries character. Four of our five mesogens turned out to show de Vries-like behavior with a layer shrinkage that is far less than that expected for conventional materials. These materials can thus be considered as the first de Vries-type materials among ionic liquid crystals., (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The orientational order parameter S2 is one of the most important quantities to describe the degree of long-range orientational ordering of liquid crystals. There are several approaches to experimentally measure this order parameter of liquid crystalline phases but every method includes substantial simplifications and assumptions. We present a simulation-based approach to elucidate the reliability of the method of Davidson, Petermann and Levelut to measure S2 via 2D X-ray experiments. We have found that this method slightly underestimates S2 by an absolute value of only 0.05 and thus provides reliable measures of S2 by X-ray diffraction., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Microorganisms move in challenging environments by periodic changes in body shape. In contrast, current artificial microrobots cannot actively deform, exhibiting at best passive bending under external fields. Here, by taking advantage of the wireless, scalable and spatiotemporally selective capabilities that light allows, we show that soft microrobots consisting of photoactive liquid-crystal elastomers can be driven by structured monochromatic light to perform sophisticated biomimetic motions. We realize continuum yet selectively addressable artificial microswimmers that generate travelling-wave motions to self-propel without external forces or torques, as well as microrobots capable of versatile locomotion behaviours on demand. Both theoretical predictions and experimental results confirm that multiple gaits, mimicking either symplectic or antiplectic metachrony of ciliate protozoa, can be achieved with single microswimmers. The principle of using structured light can be extended to other applications that require microscale actuation with sophisticated spatiotemporal coordination for advanced microrobotic technologies.

Triphenylbenzenes with different substitution patterns at the outer phenyl rings have been successfully synthesised. Sixfold n-alkoxy substitution was insufficient for mesomorphism, but already increasing the number of side chains by three methoxy groups led to liquid crystalline behaviour and mesophase formation. Symmetrical triphenylbenzenes with nine n-alkoxy side chains (≥C9) formed broad enantiotropic mesophases. The symmetry of the liquid crystalline phases was unambiguously determined by X-ray diffraction measurements as Colh and Colho for symmetry-reduced methoxy-alkoxy derivatives and symmetrical nona-alkoxy-triphenylbenzenes, respectively. Based on X-ray diffraction data a stacking model was proposed in which the single molecules aggregate to helical columns forming a mesophase.

Gelled complex fluids are soft materials in which the microstructure of the complex fluid is combined with the mechanical stability of a gel. To obtain a gelled complex fluid one either adds a gelator to a complex fluid or replaces the solvent in a gel by a complex fluid. The most prominent example of a "natural" gelled complex fluid is the cell. There are various strategies by which one can form a gelled complex fluid; one such strategy is orthogonal self-assembly, that is, the independent but simultaneous formation of two coexisting self-assembled structures within one system. The aim of this Review is to describe the structure and potential applications of various man-made gelled complex fluids and to clarify whether or not the respective system is formed by orthogonal self-assembly., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The use of non-ionic LC phases as anisotropic matrices for E/Z-isomerization of azo-guest molecules is often restricted due to limited solubilities and demixing effects. In this study we therefore employed an ionic liquid crystal (ILC) matrix to follow the photo-induced E/Z-isomerization of ionic mesogenic azobenzene guanidinium guests. The latter were prepared from 4-hydroxy-4'-(octyloxy)azobenzene, which was first treated with N-(bromoalkyl)phthalimides to introduce the spacer with varying chain length. Removal of phthalimide and final reaction with a formamidinium salt linked the ionic head group to the photoisomerizable azobenzene unit. Investigation of the mesomorphic behaviour revealed for all azobenzene ILCs smectic A mesophases with high translational order parameters and partial bilayers, as could be stated by layer spacing d. Similar packing behaviour was found for the solid state by X-ray crystal structure analysis. E/Z-isomerization of azobenzene ILCs which were completely miscible with the ionic LC phase of C12MIM-Br as anisotropic host was induced by irradiation with UV light and the reisomerization observed by time-resolved UV-Vis spectroscopy. For comparison, water was used as isotropic host. Z/E-reisomerization activation energies exhibited similar values of 97-100 kJ mol(-1) irrespective of spacer lengths and the type of host. The results demonstrate that a proper match of steric requirements of host and guest as well as layer spacings are needed for a decreased activation energy.

In contrast to common ferroelectric smectic C* liquid crystals, the siloxane-terminated smectic mesogen E6 is characterized by an unusual temperature variation of the spontaneous polarization. The polarization starts to grow from nearly zero despite the first-order SmA*-SmC* transition, and increases faster than linearly over a large temperature interval while the tilt angle rapidly saturates. To study this behavior in more detail, binary mixtures of different concentrations of E6 in the achiral SmC material C8Cl, which has a similar chemical structure, were investigated. Surprisingly, all mixtures show a temperature dependent polarization sign inversion, which shifts towards the SmC*-SmA* transition with increasing E6 concentration. For the pure E6 the inversion temperature meets the SmA*-SmC* phase transition temperature. In a second binary mixture with E6 and a conventional material C9-2PhP we found out, that the dependence of the inversion temperature on the concentration of E6 changes qualitatively when the nanosegregation is partially destroyed. A molecular theory of the polarization sign inversion in smectics C* with strong polar intermolecular interactions is developed which enables one to explain the concentration dependence of the inversion temperature in both mixtures., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

On the basis of thorough analysis of 2D X-ray diffraction patterns from smectic monodomains, we examine the influence of orientational fluctuations on the weakly first-order smectic A (SmA) to smectic C (SmC) transitions in two nonchiral organosiloxane "de Vries"-type liquid crystals. We find that these materials exhibit very large molecular tilt fluctuations with magnitudes of up to 35°--thus larger than the average tilt itself. This is essential to understand the underlying molecular mechanism behind the practical absence of smectic layer contraction in these materials: in the SmA phase, the nematic order parameter is very low (molecular fluctuations correspondingly high), and the expected layer shrinkage at the SmA to SmC transition is almost fully compensated by the increase in orientational order, as the fluctuations diminish with decreasing temperature. In addition to the general tilt fluctuations, we observe intrinsic soft-mode fluctuations. They have a λ-shaped temperature dependence that peaks at the SmA-SmC transition with a maximum amplitude of about 2°., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Several new calamitic liquid-crystalline (LC) materials with flexible hydrophilic chains, namely either hydroxy groups or ethylene glycol units, or both types together, have been synthesized in order to look for new functional LC materials exhibiting both, thermotropic and lyotropic behaviour. Such materials are of high potential interest for challenging issues such as the self-organization of carbon nanotubes or various nanoparticles. Thermotropic mesomorphic properties have been studied by using polarizing optical microscopy, differential scanning calorimetry and X-ray scattering. Four of these nonchiral and chiral materials exhibit nematic and chiral nematic phases, respectively. For some molecular structures, smectic phases have also been detected. A contact sample of one of the prepared compounds with diethylene glycol clearly shows the lyotropic behaviour; namely a lamellar phase was observed. The relationship between the molecular structure and mesomorphic properties of these new LCs with hydrophilic chains is discussed.

We present a study on the effect of added CsCl and of temperature variation on the chiral induction in a chiral nematic lyotropic liquid crystal (LC) composed of the surfactant cesium perfluorooctanoate (CsPFO), water, and the chiral dopant d-Leucine (d-Leu). The chiral induction was measured as the helical pitch P. The role of the additives CsCl and d-Leu on the phase behavior is investigated and discussed. The thermal stabilization effect of CsCl is shown to lead to an apparent salt effect on the pitch when the pitch is compared at a constant temperature. This apparent effect is removed by comparing the pitch measured for different salt concentrations at a temperature relative to the phase-transition temperatures; thus, the real salt effect on the pitch is described. High salt concentrations are shown to increase the pitch, that is, hinder the chiral induction. The effect is discussed in terms of a decreased solubilization of the amphiphilic chiral solute d-Leu in the micelles due to the salt-induced screening of the surfactant head groups and the consequential denser packing of the surfactants. The temperature variation of the pitch is investigated for all CsCl concentrations and is found to be essentially independent of the salt concentration. The temperature variation is analyzed and discussed in the context of a theoretical model taking into account specific properties of lyotropic liquid crystals. A hyperbolic decrease of the pitch is found with increasing temperature, which is known, from thermotropic liquid crystals, to stem from pretransitional critical fluctuations close to the lamellar phase. However, the experimental data confirmed the theoretical prediction that, at high temperature, that is, far away from the transition into the lamellar phase, the pitch is characterized by a linear temperature dependence which is determined by a combination of steric and dispersion chiral interactions. The parameters of the theoretical expression for the pitch have been determined by fitting the experimental data. The analysis of the salt concentration dependence of these parameters indicates that the chiral induction mechanism of d-Leu is dominated by chiral steric interactions.

Dibenzo[18]crown-6 derivatives 1 with two lateral tetraalkyloxy o-terphenyl units were prepared and converted to the corresponding complexes KX1 (X = halide, BF(4), PF(6), SCN) and NH(4)PF(6)1. Complexation was probed by MALDI-TOF spectrometry and NMR spectroscopy. Downfield shifts of (1)H NMR signals for complexes with soft anions Br, I, SCN, and PF(6) indicated the presence of tight ion pairs, whereas complexes with hard anions F, Cl, or BF(4) showed no or little shifts. In (13)C NMR spectra, upfield shifts were detected for soft anions. The character of the anion also influenced the mesomorphic properties of complexes MX1 (M = K, NH(4)), which were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and XRD in comparison to neat 1. Hard anions slightly stabilize or even destabilize the mesophase. Soft anions, however, improve the mesomorphic properties yielding mesophases with up to 70 degrees C phase widths in the case of KI1, KPF(6)1, and NH(4)PF(6)1. For complexes KSCN1 with a soft and bridging anion, the balance between mesophase stabilization and high order is shifted in favor of the plastic crystal phase.

We investigated the electrolyte effects on the stability of nematic and lamellar lyotropic liquid crystalline (LLC) phases formed by the simple anionic surfactant cesium pentadecafluorooctanoate (CsPFO) in water. To the lyotropic guest phase, at the constant CsPFO-mass fraction of 0.55, the series of electrolytes LiCl, NaCl, KCl, CsCl, CsI, and Cs(2)SO(4), respectively, was added at concentrations ranging from 0.5 to 2.5 mol %. With increasing electrolyte concentration two substantially different effects were observed. At low concentrations all added electrolytes caused an increase of the thermal stability of the LLC phases, favoring the lamellar phase over the nematic phase. This behavior is, at least qualitatively, understood within the packing parameter model. The extent of the stabilization clearly depends on the chemical nature of the added cation. For a given cation, however, the effect is colligative, i.e., independent of the chemical nature of the added anion. At higher salt concentrations a salting-out-like phase separation was induced. This effect is clearly ion-specific as the salting-out concentration varied for each cation following the order of the Hofmeister series for cations.

Most associate liquid crystals with their everyday use in laptop computers, mobile phones, digital cameras, and other electronic devices. However, in contrast to their rodlike (calamitic) counterparts, first described in 1907 by Vorländer, disklike (discotic, columnar) liquid crystals, which were discovered in 1977 by Chandrasekhar et al., offer further applications as a result of their orientation in the columnar mesophase, making them ideal candidates for molecular wires in various optical and electronic devices such as photocopiers, laser printers, photovoltaic cells, light-emitting diodes, field-effect transistors, and holographic data storage. Beginning with an overview of the various mesophases and characterization methods, this Review will focus on the major classes of columnar mesogens rather than presenting a library of columnar liquid crystals. Emphasis will be given to efficient synthetic procedures, and relevant mesomorphic and physical properties. Finally, some applications and perspectives in materials science and molecular electronics will be discussed.

Unsymmetrical benzo[15]crown-5 ethers 5 with one lateral ortho-terphenyl unit bearing alkoxy side chains of varying chain lengths (C5-C14) were prepared from 3,4-dialkoxyphenylbromides 2. Complexation with metal salts MX (M = Na, Cs) afforded the corresponding derivatives MX5. The uncomplexed crown ethers 5 h and 5 i, with dodecyloxy and tetradecyloxy side chains, respectively, exhibit liquid crystalline properties. In the series of complexed crown ethers, liquid crystal properties appeared as early as NaI5 f with C9H19 side chains. Whereas the uncomplexed 5 h,i form smectic mesophases, the complexed NaI5 g and NaI5 h exhibit textures typical of columnar mesophases. These results were supported by X-ray diffraction measurements (WAXS, SAXS), which revealed smectic (5 h,i), rectangular columnar (NaI5 g), and hexagonal columnar (NaI5 h) mesophases. As the liquid crystalline phase might retain packing features of the solid-state structure, single-crystal X-ray analyses were also performed for some of the uncomplexed and complexed crown ether derivatives. The complex NaI(3)5 a displays a sandwich-type structure, with the crown ether cores mutually antiperiplanar and maintaining an almost perfect crown conformation. In contrast, non-mesogenic uncomplexed crown ether 5 b displays a layer-type ordering in the solid phase.

The thermotropic smectic phases of amphiphilic 2-(trans-4-n-alkylcyclohexyl)-propane-1,3-diols were investigated by means of small- and wide-angle x-ray scattering and values of the smectic (bi-)layer spacing, the orientational order parameters P(2) and P(4), the orientational distribution function as well as the intralayer correlation length were extracted from the scattering profiles. The results for the octyl homolog indicate that these smectic phases combine a very high degree of smectic one-dimensional-translational order with remarkably low orientational order, the order parameter of which (P(2) approximately 0.56) is far below those values typically found in nonamphiphilic smectics. This combination, quite exceptional in thermotropic smectics, most likely originates from the intermolecular hydrogen bonding between the terminal diol groups which seems to be the specific driving force in the formation of the thermotropic smectic structure in these amphiphiles and leads to a type of microphase segregation. Even in the absence of a solvent, the liquid-crystalline ordering of the amphiphilic mesogens comes close to the structure of the so-called neat soaps, found in lyotropic liquid crystals.

By mixing the achiral liquid crystal HOAB, exhibiting a nematic (N)-smectic-C (SmC) mesophase sequence, with the chiral antiferroelectric liquid crystal (AFLC) (S,S)-M7BBM7, forming the antiferroelectric SmC(a)(*) phase, at least seven different mesophases have been induced which neither component forms on its own: a twist-grain-boundary (TGB(*)) phase, two or three blue phases, the untilted SmA(*) phase, as well as all three chiral smectic-C-type "subphases," SmC(alpha)(*), SmC(beta)(*), and SmC(gamma)(*). The nature of the induced phases and the transitions between them were determined by means of optical and electro-optical investigations, dielectric spectroscopy, and differential scanning calorimetry. The induced phases can to a large extent be understood as a result of frustration, TGB(*) at the border between nematic and smectic, the subphases between syn and anticlinic tilted smectic organization. X ray scattering experiments reveal that the smectic layer spacing as well as the degree of smectic order is relatively constant in the whole mixture composition range in which AFLC behavior prevails, whereas both these parameters rapidly decrease as the amount of HOAB is increased to such an extent that no other smectic-C-type phase than SmC/SmC(*) exists. By tailoring the composition we are able to produce liquid crystal mixtures exhibiting unusual phase sequences, e.g., with a direct isotropic-SmC(a)(*) transition or a temperature range of the SmC(beta)(*) subphase of about 50 K.

A non-layer-shrinkage fluorinated ferroelectric liquid crystal compound, 8422[2F3], has been characterized by means of optical, x-ray, and calorimetric methods. The orientational distribution within macroscopic volumes, determined through wide-angle x-ray scattering and birefringence measurements, was found to be identical in the Sm-A* and helical Sm-C* phases. Together with the absence of layer shrinkage, this constitutes strong evidence that the second-order Sm-A*-Sm-C* transition in this material is well described by the diffuse cone model of de Vries. The absolute values of the layer spacing show that the molecules aggregate to antiparallel pairs. The molecular interaction across the layer boundaries will then occur only between fluorine atoms, leading to unusually weak interlayer tilt direction correlation. This explains the experimental observations of a very easily disturbed Sm-C* helix and a peculiar surface-stabilized texture. Tilt angle and birefringence values as a function of field and temperature have been evaluated in the Sm-A* and Sm-C* phases and the results corroborate the conclusions from the x-ray investigations.