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The twist-bend nematic liquid crystal phase is a three-dimensional fluid in which achiral bent molecules spontaneously form an orientationally ordered, macroscopically chiral, heliconical winding of a ten nanometer-scale pitch in the absence of positional ordering. Here, the structure of the twist-bend phase of the bent dimer CB7CB and its mixtures with 5CB is characterized, revealing a hidden invariance of the self-assembly of the twist-bend structure of CB7CB, such that over a wide range of concentrations and temperatures, the helix pitch and cone angle change as if the ground state for a pitch of the TB helix is an inextensible heliconical ribbon along the contour formed by following the local molecular long axis (the director). Remarkably, the distance along the length for a single turn of this helix is given by 2πRmol, where Rmol is the radius of bend curvature of a single all-trans CB7CB molecule. This relationship emerges from frustrated steric packing due to the bent molecular shape: space in the fluid that is hard to fill attracts the most flexible molecular subcomponents, a theme of nanosegregation that generates self-assembled, oligomer-like correlations of interlocking bent molecules in the form of a brickwork-like tiling of pairs of molecular strands into duplex double-helical chains. At higher temperatures in the twist-bend phase, the cone angle is small, the director contour is nearly along the helix axis z, and the duplex chains are sequences of biaxial elements formed by overlapping half-molecule pairs, with an approximately 45° rotation of the biaxis between each such element along the chain.

We have structurally characterized the liquid crystal (LC) phase that can appear as an intermediate state when a dielectric nematic, having polar disorder of its molecular dipoles, transitions to the almost perfectly polar-ordered ferroelectric nematic. This intermediate phase, which fills a 100-y-old void in the taxonomy of smectic LCs and which we term the "smectic ZA," is antiferroelectric, with the nematic director and polarization oriented parallel to smectic layer planes, and the polarization alternating in sign from layer to layer with a 180 Å period. A Landau free energy, originally derived from the Ising model of ferromagnetic ordering of spins in the presence of dipole-dipole interactions, and applied to model incommensurate antiferroelectricity in crystals, describes the key features of the nematic-SmZA-ferroelectric nematic phase sequence.

We have structurally characterized the liquid crystal (LC) phase that can appear as an intermediate state when a dielectric nematic, having polar disorder of its molecular dipoles, transitions to the almost perfectly polar-ordered ferroelectric nematic. This intermediate phase, which fills a 100-y-old void in the taxonomy of smectic LCs and which we term the "smectic ZA," is antiferroelectric, with the nematic director and polarization oriented parallel to smectic layer planes, and the polarization alternating in sign from layer to layer with a 180 Å period. A Landau free energy, originally derived from the Ising model of ferromagnetic ordering of spins in the presence of dipole-dipole interactions, and applied to model incommensurate antiferroelectricity in crystals, describes the key features of the nematic-SmZA-ferroelectric nematic phase sequence. [ABSTRACT FROM AUTHOR]

We report the observation of the smectic AF, a liquid crystal phase of the ferroelectric nematic realm. The smectic AF 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 × 105 V/m is observed. The SmAF phase appears upon cooling in two binary mixtures of partially fluorinated mesogens: 2N/DIO, exhibiting a nematic (N)–smectic ZA (SmZA)–ferroelectric nematic (NF)–SmAF phase sequence, and 7N/DIO, exhibiting an N–SmZA–SmAF phase sequence. The latter presents an opportunity to study a transition between two smectic phases having orthogonal systems of layers. [ABSTRACT FROM AUTHOR]

The organic mesogens RM734 and DIO are members of separate molecular families featuring distinct molecular structures. These families are the first ones known to exhibit a ferroelectric nematic liquid crystal phase. Here, we present an experimental investigation of the phase diagram and electro-optics of binary mixtures of RM734 and DIO. We observe paraelectric nematic and ferroelectric nematic phases in both materials, each of which exhibits complete miscibility across the phase diagram, showing that the paraelectric and ferroelectric are the same phases in RM734 and DIO. Remarkably, these molecules form ideal mixtures with respect to both the paraelectric–ferroelectric nematic phase behaviour and the ferroelectric polarisation density of the mixtures, the principal order parameter of the transition. Ideal mixing is also manifested in the orientational viscosity, and the onset of glassy dynamics at low temperature. This behaviour is attributable in part to the similarity of their overall molecular shape and net longitudinal dipole moment, and to a common tendency for head-to-tail molecular association. In contrast, the significant difference in molecular structures leads to poor solubility in the crystal phases, enhancing the stability of the ferroelectric nematic phase at low temperature in the mixtures and enabling room-temperature electro-optic effects. [ABSTRACT FROM AUTHOR]

Recently, the topographic patterning of surfaces by lithography and nanoimprinting has emerged as a new and powerful tool for producing single structural domains of liquid crystals and other soft materials. Here the use of surface topography is extended to the organization of liquid crystals of bent-core molecules, soft materials that, on the one hand, exhibit a rich, exciting, and intensely studied array of novel phases, but that, on the other hand, have proved very difficult to align. Among the most notorious in this regard are the polarization splay modulated (B7) phases, in which the symmetry-required preference for ferroelectric polarization to be locally bouquet-like or 'splayed' is expressed. Filling space with splay of a single sign requires defects and in the R7 splay is accommodated in the form of periodic splay stripes spaced by defects and coupled to smectic layer undulations. Upon cooling from the isotropic phase this structure grows via a first order transition in the form of an exotic array of twisted filaments and focal conic defects that are influenced very little by classic alignment methods. By contrast, growth under conditions of confinement in rectangular topographic channels is found to produce completely new growth morphology, generating highly ordered periodic layering patterns. The resulting macroscopic order will be of great use in further exploration of the physical properties of bent-core phases and offers a route for application of difficult-to-align soft materials as are encountered in organic electronic and optical applications. topographical confinement | monodomain | banana shaped | anchoring doi/ 10.1073/pnas.1014593107

In high-resolution adiabatic scanning calorimetry (ASC) experiments, data for the temperature dependence of the specific enthalpy, h(T), and of the specific heat capacity, cp(T), are simultaneously obtained, from which the order of the phase transition and critical behaviour can be evaluated. ASC was applied to study the nematic to ferroelectric nematic phase transition (N–NF) in the liquid crystal molecule 4-[(4-nitrophenoxy)carbonyl]phenyl 2,4-dimethoxybenzoate (RM734). The N–NF was found to be very weakly first order with a latent heat Δh = 0.115 ± 0.005 J/g. The pretransitional specific heat capacity behaviour is substantially larger in the high-temperature N phase than in the low-temperature NF phase. In both phases the power-law analysis of cp(T) resulted in a critical exponent α = 0.50 ± 0.05 and amplitude ratio ANF/AN = 0.42 ± 0.03. The very small latent heat and the value of α indicate that the N–NF transition is close to a tricritical point. This is confirmed by a value of the order parameter exponent β ≈ 0.25, recently obtained from electric polarisation measurements. Invoking two-scale-factor universality, it follows from the low value of ANF/AN ratio that the size of the critical fluctuations is much larger in the NF phase than in the N phase. [ABSTRACT FROM AUTHOR]

The recently discovered ferroelectric nematic (NF) liquid crystals (LCs) with over 0.04 C m−2 ferroelectric polarization and 104 relative dielectric constants, coupled with sub‐millisecond switching, offer potential applications in high‐power super capacitors and low voltage driven fast electro‐optical devices. This paper presents electrical, optical, and electro‐optical studies of a ferroelectric nematic LC material doped with commercially available chiral dopants. While the NF phase of the undoped LC is only monotropic, the chiral NF phase is enantiotropic, indicating a chirality induced stabilization of the polar nematic order. Compared to undoped NF material, a remarkable improvement of the electro‐optical switching time is demonstrated in the chiral doped materials. The color of the chiral mixtures that exhibit a selective reflection of visible light in the chiral NF phase, can be reversibly tuned by 0.02–0.1 V µm−1 in‐plane electric fields, which are much smaller than typically required in full‐color cholesteric LC displays and do not require complicated driving scheme. The fast switchable reflection color at low fields has potential applications for LC displays without backlight, smart windows, shutters, and e‐papers. [ABSTRACT FROM AUTHOR]

We show that surface interactions can vectorially structure the three-dimensional polarization field of a ferroelectric fluid. The contact between a ferroelectric nematic liquid crystal and a surface with in-plane polarity generates a preferred in-plane orientation of the polarization field at that interface. This is a route to the formation of fluid or glassy monodomains of high polarization without the need for electric field poling. For example, unidirectional buffing of polyimide films on planar surfaces to give quadrupolar in-plane anisotropy also induces macroscopic in-plane polar order at the surfaces, enabling the formation of a variety of azimuthal polar director structures in the cell interior, including uniform and twisted states. In a p-twist cell, obtained with antiparallel, unidirectional buffing on opposing surfaces, we demonstrate three distinct modes of ferroelectric nematic electro-optic response: intrinsic, viscosity-limited, field-induced molecular reorientation; field-induced motion of domain walls separating twisted states of opposite chirality; and propagation of polarization reorientation solitons fromthe cell plates to the cell center upon field reversal. Chirally doped ferroelectric nematics in antiparallelrubbed cells produce Grandjean textures of helical twist that can be unwound via field-induced polar surface reorientation transitions. Fields required are in the 3-V/mm range, indicating an in-plane polar anchoring energy of wP ~3 × 10-3 J/m². [ABSTRACT FROM AUTHOR]

We report the experimental determination of the structure and response to applied electric field of the lower-temperature nematic phase of the previously reported calamitic compound 4-[(4-nitrophenoxy)carbonyl]phenyl2,4-dimethoxybenzoate (RM734). We exploit its electro-optics to visualize the appearance, in the absence of applied field, of a permanent electric polarization density, manifested as a spontaneously broken symmetry in distinct domains of opposite polar orientation. Polarization reversal is mediated by field-induced domain wall movement, making this phase ferroelectric, a 3D uniaxial nematic having a spontaneous, reorientable polarization locally parallel to the director. This polarization density saturates at a low temperature value of ~6 µC/cm², the largest ever measured for a fluid or glassy material. This polarization is comparable to that of solid state ferro-electrics and is close to the average value obtained by assuming perfect, polar alignment of molecular dipoles in the nematic. We find a host of spectacular optical and hydrodynamic effects driven by ultra-low applied field (E ~ 1 V/cm), produced by the coupling of the large polarization to nematic birefringence and flow. Electrostatic selfinteraction of the polarization charge renders the transition from the nematic phase mean field-like and weakly first order and controls the director field structure of the ferroelectric phase. Atomistic molecular dynamics simulation reveals short-range polar molecular interactions that favor ferroelectric ordering, including a tendency for head-to-tail association into polar, chain-like assemblies having polar lateral correlations. These results indicate a significant potential for transformative, new nematic physics, chemistry, and applications based on the enhanced understanding, development, and exploitation of molecular electrostatic interaction. [ABSTRACT FROM AUTHOR]

The initial development of photoinduced anisotropy in highly photosensitive monolayers of an aminoazobenzene molecule (dMR, a derivative of o-methyl red) that are initially randomized using circularly polarized light is found to be significantly slower than in monolayers randomized by thermal relaxation. We propose that this is a direct consequence of the slow thermal relaxation of isomers from the cis to the trans state and suggest that such considerations are important in designing even more sensitive photoactive monolayers and in understanding their photodynamics. [ABSTRACT FROM AUTHOR]

The helical nanofilament (HNF) and low‐temperature dark conglomerate (DC) liquid‐crystal (LC) phases of bent‐core molecules show the same local layer structure but present different bulk morphologies. The DC phase is characterized by the formation of nanoscale toric focal conics, whereas the HNF phase is constructed of bundles of twisted layers. Although the local layer structure is similar in both phases, materials that form these phases tend to form one morphology in preference to the other. Targeted control of the nanostructures would provide pathways to potential applications and insight into how conditions drive a specific phase formation. Here, W624, a compound known to form the DC phase is confined in nanometer scale channels of porous anodized aluminum oxide (AAO) membranes. Within each nanochannel, the DC phase is suppressed forming the HNF structure instead, indicating the nanoscale spatial limitation can control the phase structure of the DC phase. [ABSTRACT FROM AUTHOR]

We describe the design and synthesis of a ferroelectric liquid crystal composed of racemic molecules. The ferroelectric polarization results from spontaneous polar symmetry breaking in a fluid smectic. The ferroelectric phase is also chiral, resulting in the formation of a mixture of macroscopic domains of either handedness at the isotropic-to-liquid crystal phase transition. This smectic liquid crystal is thus a fluid conglomerate. Detailed investigation of the electrooptic and polarization current behavior within individual domains in liquid crystal cells shows the thermodynamically stable structure to be a uniformly tilted smectic bow-phase (banana phase), with all layer pairs homochiral and ferroelectric (Sm[C.sub.S] [P.sub.F])., Ferroelectric liquid crystals (FLCs) have been a wellspring of fruitful scientific investigation and innovation since Meyer first postulated, then proved, the polar ordering in chiral smectics (1), and Clark and [...]

The results of an investigation, which shows that the chirality of SmC phase derives from surface interactions, are described. No evidence for the presence of a ferroelectric polarization in the SmC phase of 4'-octyloxyphenyl-4-octyloxybenzoate, a necessary result of chiral symmetry of the phase, could be found, even though very sensitive tests for such polarization are applied.

We have previously reported the first realization of an orthogonal ferroelectric bent-core SmAPF phase by directed design in mesogens with a single tricarbosilane-terminated alkoxy tail. Given the potentially useful electrooptic properties of this phase, including analog phase-only electrooptic index modulation with optical latching, we have been exploring its "structure space", searching for novel SmAPF mesogens. Here, we report two classes of these--the first designed to optimize the dynamic range of the index modulation in parallel-aligned cells by lowering the bend angle of the rigid core, and the second expanding the structure space of the phase by replacing the tricarbosilane-terminated alkyl tail with a polyfluorinated polyethylene glycol oligomer. [ABSTRACT FROM AUTHOR]

We report the synthesis and properties of several new heliconical twist-bend nematic (NTB) bimesogens possessing “classic” bent-core benzylideneaniline wings combined with oligomethylene spacers of odd parity. While short alkoxy tails combined with a resorcinol diester core in the classic system appear to give SmA phases (not B2 phases), in the present system, methoxy or ethoxy tails exhibit the NTBphase as evidenced by textural analysis. Several of these compounds also exhibit microscopic helical defect structures in the NTBphase, which have been reported in other lamellar and pseudo-lamellar liquid crystal phases, but not in the NTBphase. [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]

Bent-core liquid crystals show a variety of novel structures involving the interplay of molecular bend, tilt and polarisation. Here we investigate the microstructures of the B4, B7 and the dark conglomerate (DC) phases at the air/liquid crystal interface. In these phases, bent-core molecules undergo complex self-assembly, forming helical nanofilaments (the B4 phase), layer undulations (the B7 phase) and disordered focal conics (the DC phase) in the bulk. However, due to the fluidity of the phases and the homeotropic alignment at the interface, several different topographies are observed at the air/liquid crystal interface. We will discuss the surface structures discovered so far in the B4, B7 and DC phases and show how they help us to understand the microstructure and the self-assembly of the liquid crystal phases of bent-core molecules. [ABSTRACT FROM PUBLISHER]

Freeze-fracture transmission electron microscopy study of the nanoscale structure of the so-called "twist-bend" nematic phase of the cyanobiphenyl (CB) dimer molecule CB(CH2)7CB reveals stripe-textured fracture planes that indicate fluid layers periodically arrayed in the bulk with a spacing of d ∼ 8.3 nm. Fluidity and a rigorously maintained spacing result in long-range-ordered 3D focal conic domains. Absence of a lamellar X-ray reflection at wavevector q ∼ 2π/d or its harmonics in synchrotron-based scattering experiments indicates that this periodic structure is achieved with no detectable associated modulation of the electron density, and thus has nematic rather than smectic molecular ordering. A search for periodic ordering with d ∼ in CB(CH2)7CB using atomistic molecular dynamic computer simulation yields an equilibrium heliconical ground state, exhibiting nematic twist and bend, of the sort first proposed by Meyer, and envisioned in systems of bent molecules by Dozov and Memmer. We measure the director cone angle to be ϑTB ∼ 25° and the full pitch of the director helix to be pTB ∼ 8.3 nm, a very small value indicating the strong coupling of molecular bend to director bend. [ABSTRACT FROM AUTHOR]

Study of the optical symmetry of the high-temperature liquid crystal phase of the bent core molecule NORABOW produces the first direct evidence for a material having fluid layers with internally stabilised triclinic symmetry, exhibiting the SmCPG structure: spontaneous in-plane polar ordering as well as substantial coherent molecular tilt in two Euler angles, giving an optical dielectric tensor with none of the principal axes oriented in or normal to the layer plane. The resulting C1 symmetry makes NORABOW layers the least symmetric fluids. This triclinic layer structure is found to be robust, depending little on the relative state of neighbouring layers or position relative to the air interface. [ABSTRACT FROM AUTHOR]

We report the synthesis of organic polymer optical fibers with the following interesting supermolecular stereochemistry: 1)A thermodynamically stable macroscopic polar axis oriented approximately normal to the fiber axis: and 2) A nonlinear optical (NLO) chromophore oriented along the polar axis. Such a polymer fiber has been created using a main-chain ferroelectric liquid crystal polymer (FLCP) frozen in the glassy state at room temperature. The material is composed of "side-by-side twin" mesogens wherein the DR-1 NLO chromophore is oriented normal to the director. The polymer, which possesses excellent liquid crystal and glass transition temperatures for the present study, was prepared by acyclic diene metathesis polymerization of a liquid crystal diene. Details of the layer and director structure in the FLCP glasses are under investigation. [ABSTRACT FROM AUTHOR]

A simple procedure for the preparation of octadecylsiloxane self-assembled monolayers (SAMs) on float glass substrates is described. The method utilizes commercial octadecyltriethoxysilane, OTE: n -C 18 H 37 Si(OCH 2 CH 3 ) 3 , as the SAM precursor, with deposition accomplished in toluene solution using n -butylamine as catalyst. This synthetic approach obviates the use of the problematic trichlorosilanes typically required for the preparation of high quality SAMs, and is characterized by a wide 'process window,' utilizing off-the-shelf reagents without special handling. [ABSTRACT FROM AUTHOR]

We describe a device geometry using interdigital electrodes that enables the electrically driven reorientation of smectic A layers from a homeotropic state (dark between crossed polarizers) to a planar state (bright between crossed polarizers) and back again. The resulting electro-optic effect is strongly bistable and gives high contrast ratio and fast response, rendering it a potential candidate for flexible-display applications. [ABSTRACT FROM AUTHOR]

We have identified a metastable liquid-crystal (LC) structure in the de Vries smectic-A* phase (de Vries Sm-A*) formed by silicon-containing molecules under certain boundary conditions. The phase transition with the metastable structure was observed in a LC droplet placed on a planar aligned substrate and LCs confined in the groove of a silicon microchannel. During the rapid cooling step, a batonnet structure was generated as an intermediate and metastable state prior to the transition that yielded the thermodynamically stable toric focal conic domains. This distinctive behavior was characterized using depolarized reflection light microscopy and grazing incidence x-ray diffraction techniques. We concluded that the silicon groups in the molecules that formed the de Vries phase induced the formation of layered clusters called cybotactic structures. This observation is relevant to an exploration of the physical properties of cybotactic de Vries phases and gives a hint as to their optoelectronic applications. [ABSTRACT FROM AUTHOR]

We describe the unusual electro-optic response of a biaxial bent-core liquid crystal molecule that exhibits an anticlinic, antiferroelectric smectic phase (Sm-CA/PA) with a molecular tilt angle close to 45°. In the ground state, the sample shows very low birefringence. A weak applied electric field distorts the antiferroelectric ground state, inducing a small azimuthal reorientation of the molecules on the tilt cone. This results in only a modest increase in the birefringence but an anomalously large (∼40°) analog rotation of the extinction direction. This unusual electro-optic response is shown to be a consequence of the molecular biaxiality. [ABSTRACT FROM AUTHOR]

A smectic-A (SmA) liquid crystal phase of fluid layers with in-plane polarization P is shown to exhibit effective conductivity in the semiconducting range during electric-field-induced polarization reorientation, but becomes insulating once the polarization is aligned with the field. Such fluid ferroelectrics sandwiched between highly insulating layers enable electro-optic devices with long-term dc electrostatic control of polarization and optic axis orientation. [ABSTRACT FROM AUTHOR]