On the Nature of the B4 Banana Phase: Crystal or Not a Crystal?

Bent-core or banana-shaped liquid crystal mesogens are known to form chiral smectic phases from achiral or racemic molecules, representing the first example of conglomerate formation in bulk fluids. The most well studied examples of this behavior occur in the SmCP phases, subphases possessing the B2 chiral layer structure. However, the first description of chirality in the banana phase space was of the B4 phase, whose detailed structure is still under investigation. Indeed, the B4 phase is quite unique, and a consensus regarding the question of whether this phase is crystalline or liquid crystalline has not been reached. Here we describe data showing distinct differences, by NMR, between the SmCP phase and B4 phase of the prototypical banana phase mesogen NOBOW and, based upon an analysis of these data, suggest that the B4 phase is an unusual type of crystalline solid

A Chameleon Chiral Polar Liquid Crystal: Rod-Shaped When Nematic, Bent-Shaped When Smectic

The first antiferroelectric liquid crystal (AFLC) exhibiting a (chiral) nematic phase, a combination which has long been the goal of synthetic chemists working with polar liquid crystals but which at the same time represents a fundamental contradiction in terms of translational order, was recently reported by Nishiyama and co-workers. We have investigated this chiral twin dimer by optic, electrooptic, and dielectric methods and conclude that it is not an ordinary AFLC material, but one where the peculiar properties of bent-core smectics are combined with those of ordinary rod-shaped liquid crystals. The compound exhibits a new type of nematic−smectic phase transition, connected with a change of molecule conformation from rod- to bent-shaped. This also has an important impact on the chiral interactions in the system. Toward the high-temperature end of the smectic phase, the energy balance between bent conformation smectic and straight conformation nematic can be shifted by an electric field such that the transition to the nematic phase with stretched-out molecules can be field-induced

Ferroelectric Liquid Crystals for Nonlinear Optics: Orientation of the Disperse Red 1 Chromophore along the Ferroelectric Liquid Crystal Polar Axis^†

Ferroelectric Liquid Crystals for Nonlinear Optics:  Orientation of the Disperse Red 1 Chromophore along the Ferroelectric Liquid Crystal Polar Axis†</sup

Charge Generation Measured for Fullerene–Helical Nanofilament Liquid Crystal Heterojunctions

The helical nanofilament (HNF) liquid crystal phase is an ordered architecture exhibiting interesting properties for charge transport. It is a small molecule self-assembly of stacked and twisted crystalline layers, which form alignable organic nanorods with half the surface area of the filaments consisting of aromatic sublayer edges. HNFs mixed with an electron acceptor generate an intriguing network for photoinduced electron transfer (PET). In this work, we characterize the structure of the HNF phase as processed into thin films with transmission electron microscopy (TEM) and X-ray diffraction (XRD). Additionally, we measure the flash-photolysis time-resolved microwave conductivity (TRMC) in samples where the HNF phase is fabricated into heterojunctions with the fullerenes C60 and PC60BM, prototypical electron acceptors for organic photovoltaics. Two distinct microstructures of the thin films were identified and compared for PET. A near-unity charge generation yield is observed in a bilayer of HNFs with C60. Moreover, the HNF phase is shown to be 10× better at charge generation than a lamellar structuring of the same components. Thus, the HNF phase is shown to be a good charge-generation interface

Ferroelectric Liquid Crystals for Nonlinear Optics: Orientation of the Disperse Red 1 Chromophore along the Ferroelectric Liquid Crystal Polar Axis^†

Ferroelectric Liquid Crystals for Nonlinear Optics:  Orientation of the Disperse Red 1 Chromophore along the Ferroelectric Liquid Crystal Polar Axis†</sup

Reflection Symmetry Breaking in Achiral Rod-Shaped Smectic Liquid Crystals?

The SmC phase of 4‘-octyloxyphenyl-4-octyloxybenzoate has been examined in light of recent reports that this phase is chiral. The results suggest that two varieties of chiral domains in LC cells of the phenylbenzoate are indeed formed, driven by interactions with surfaces. Application of sensitive probes for chirality and polarity in the absence of such interfacial influences failed to find any. Currently, there is no evidence that the subject SmC phase is chiral

Photo-Reversible Liquid Crystal Alignment using Azobenzene-Based Self-Assembled Monolayers: Comparison of the Bare Monolayer and Liquid Crystal Reorientation Dynamics

Photosensitive surfaces treated to have in-plane structural anisotropy by illumination with polarized light can be used to orient liquid crystals (LCs). Here we report a detailed study of the dynamic behavior of this process at both short and long times, comparing the ordering induced in the bare active surface with that of the LC in contact with the surface using a high-sensitivity polarimeter that enables detailed characterization of the anisotropy of the active surface. The experiments were carried out using self-assembled monolayers (SAMs) made from dimethylaminoazobenzene covalently bonded to a glass surface through a triethoxysilane terminus. This surface gives planar alignment of the liquid crystal director with an azimuthal orientation that can be controlled by the polarization of actinic light. We find a remarkable long-term collective interaction between the orientationally ordered SAM and the director field of the LC: while an azobenzene based SAM in contact with an isotropic gas or liquid relaxes to an azimuthally isotropic state in the absence of light due to thermal fluctuations, an orientationally written SAM in contact with LC in the absence of light can maintain the LC director twist permanently, that is, the SAM is capable of providing azimuthal anchoring to the LC even in the presence of a torque about the surface normal. We find that the short-time, transient LC reorientation is limited by the weak azimuthal anchoring strength of the SAM and by the LC viscosity

Photo-Reversible Liquid Crystal Alignment using Azobenzene-Based Self-Assembled Monolayers: Comparison of the Bare Monolayer and Liquid Crystal Reorientation Dynamics

Photosensitive surfaces treated to have in-plane structural anisotropy by illumination with polarized light can be used to orient liquid crystals (LCs). Here we report a detailed study of the dynamic behavior of this process at both short and long times, comparing the ordering induced in the bare active surface with that of the LC in contact with the surface using a high-sensitivity polarimeter that enables detailed characterization of the anisotropy of the active surface. The experiments were carried out using self-assembled monolayers (SAMs) made from dimethylaminoazobenzene covalently bonded to a glass surface through a triethoxysilane terminus. This surface gives planar alignment of the liquid crystal director with an azimuthal orientation that can be controlled by the polarization of actinic light. We find a remarkable long-term collective interaction between the orientationally ordered SAM and the director field of the LC: while an azobenzene based SAM in contact with an isotropic gas or liquid relaxes to an azimuthally isotropic state in the absence of light due to thermal fluctuations, an orientationally written SAM in contact with LC in the absence of light can maintain the LC director twist permanently, that is, the SAM is capable of providing azimuthal anchoring to the LC even in the presence of a torque about the surface normal. We find that the short-time, transient LC reorientation is limited by the weak azimuthal anchoring strength of the SAM and by the LC viscosity

Understanding and Manipulating Helical Nanofilaments in Binary Systems with Achiral Dopants

Here, we report the relationship between helical pitch of the helical nanofilament (HNF) phase formed by bent-core molecule NOBOW and the concentration of achiral dopants 5CB and octane, using linearly polarized resonant soft X-ray scattering (RSoXS). Utilizing theory-based simulation, which fits well with the experiments, the molecular helices in the filament were probed and the superstructure of helical 5CB directed by groove of HNFs was observed. Quantitative pitch determination with RSoXS reveals that helical pitch variation is related to 5CB concentration with no temperature dependence. Doping rodlike immiscible 5CB led to a pitch shortening of up to 30%, which was attributed to a change in interfacial tension. By shedding light not only on phase behavior of binary systems but also enabling control over pitch length, our work may benefit various applications of HNF-containing binary systems, including optical rotation devices, circularly polarized light emitters, and chirality transfer agents