Chiroptical Performances in Self-Assembled Hierarchical Nanosegregated Chiral Intermediate Phases Composed of Two Different Achiral Bent-Core Molecules.

In this paper, chiral intermediate phases composed of two achiral molecules are fabricated by utilizing nanophase separation and molecular hierarchical self-organization. An achiral bent-core guest molecule, exhibiting a calamitic nematic and a dark conglomerate phase according to the temperature, is mixed with another achiral bent-core host molecule possessing a helical nanofilament to separate the phases between them. Two nanosegregated phases are identified, and considerable chiroptical changes, such as circular dichroism and circularly polarized luminescence, are detected at the transition temperatures between the different nanophase-separated states. The nanosegregated chiral phase-wherein the helical nanofilament and dark conglomerate phases are phase-separated-exhibits the highest chiroptical intensities. The luminescence dissymmetry factor, |glum|, in this phase is amplified by an order of magnitude compared with that of another nanosegregated phase, wherein the helical nanofilament and nematic phases are phase-separated.

Anisotropic fluid with phototunable dielectric permittivity.

Dielectric permittivity, a measure of polarisability, is a fundamental parameter that dominates various physical phenomena and properties of materials. However, it remains a challenge to control the dielectric permittivity of materials reversibly over a large range. Herein, we report an anisotropic fluid with photoresponsive dielectric permittivity (200 < ε < 18,000) consisting of a fluorinated liquid-crystalline molecule (96 wt%) and an azobenzene-tethered phototrigger (4 wt%). The reversible trans-cis isomerisation of the phototrigger under blue and green light irradiation causes a switch between two liquid-crystalline phases that exhibit different dielectric permittivities, with a rapid response time (<30 s) and excellent reversibility (~100 cycles). This anisotropic fluid can be used as a flexible photovariable capacitor that, for example, allows the reversible modulation of the sound frequency over a wide range (100 < f < 8500 Hz) in a remote manner using blue and green wavelengths.

A New Class of Chiral Nematic Phase with Helical Polar Order.

A novel chiral nematic phase with a polar helical order is realized via the introduction of helical twisting power into a polar nematogen. The properties of the induced polar nematic (polar cholesteric: Np*) phase differ from those of the conventional cholesteric (N*) phases existing thus far. Np*, which is a new class of N* structures, is characterized not only by its helically twisted nematic director, but also by a continuously twisted polarization. Transmission spectroscopy and helical pitch measurements in a wedge cell revealed that the half-helical pitch in the Np* phase vanished because of the polar response in the Np* helix. The inner polar director in the Np* phase is confirmed in dielectric and second-harmonic-generation studies. Furthermore, this unique Np*LC, which corresponds to a half-/full-pitch helix, enables ultrafast electro-optic switching (τ < 20 µs), and proposes new potential applications for electrically interchangeable photonic bandgaps.

Development of ferroelectric nematic fluids with giant-ε dielectricity and nonlinear optical properties.

Superhigh-ε materials that exhibit exceptionally high dielectric permittivity are recognized as potential candidates for a wide range of next-generation photonic and electronic devices. In general, achieving a high-ε state requires low material symmetry, as most known high-ε materials are symmetry-broken crystals. There are few reports on fluidic high-ε dielectrics. Here, we demonstrate how small molecules with high polarity, enabled by rational molecular design and machine learning analyses, enable the development of superhigh-ε fluid materials (dielectric permittivity, ε > 104) with strong second harmonic generation and macroscopic spontaneous polar ordering. The polar structures are confirmed to be identical for all the synthesized materials. Furthermore, adapting this strategy to high-molecular weight systems allows us to generalize this approach to polar polymeric materials, creating polar soft matters with spontaneous symmetry breaking.

High-Performance Polymer Dispersed Liquid Crystal Enabled by Uniquely Designed Acrylate Monomer.

The widespread electro-optical applications of polymer dispersed liquid crystals (PDLCs) are hampered by their high-driving voltage. Attempts to fabricate PDLC devices with low driving voltage sacrifice other desirable features of PDLCs. There is thus a clear need to develop a method to reduce the driving voltage without diminishing other revolutionary features of PDLCs. Herein, we report a low-voltage driven PDLC system achieved through an elegantly simple and uniquely designed acrylate monomer (A3DA) featuring a benzene moiety with a dodecyl terminal chain. The PDLC films were fabricated by the photopolymerization of mono- and di-functional acrylate monomers (19.2 wt%) mixed in a nematic liquid crystal E7 (80 wt%). The PDLC film with A3DA exhibited an abrupt decline of driving voltage by 75% (0.55 V/µm) with a high contrast ratio (16.82) while maintaining other electro-optical properties almost the same as the reference cell. The response time was adjusted to satisfactory by tuning the monomer concentration while maintaining the voltage significantly low (3 ms for a voltage of 0.98 V/µm). Confocal laser scanning microscopy confirmed the polyhedral foam texture morphology with an average mesh size of approximately 2.6 µm, which is less in comparison with the mesh size of reference PDLC (3.4 µm), yet the A3DA-PDLC showed low switching voltage. Thus, the promoted electro-optical properties are believed to be originated from the unique polymer networks formed by A3DA and its weak anchoring behavior on LCs. The present system with such a huge reduction in driving voltage and enhanced electro-optical performance opens up an excellent way for abundant perspective applications of PDLCs.

Development of a liquid crystal laser using a simple cubic liquid crystalline blue phase platform.

A liquid crystal laser using a polymer-stabilized simple cubic blue phase (BPII) platform has been scarcely reported because the polymer stabilization of a BPII is relatively difficult compared to that of a body-centered-cubic BP (BPI). In this study, we succeeded in fabricating a dye-doped polymer-stabilized BPII laser with wide operating-temperature ranges over 15 °C including room temperature. A narrow and sharp single laser peak with a full width at half maximum of approximately 2 nm was derived from the photonic band edge effect of the BPII-distributed feedback optical resonator. As a result, the laser emission was a circularly polarized light, which matched the chirality of the proposed pure BPII.

Substituent effects of bridged binaphthyl-type chiral dopants on the helical twisting power in dopant-induced chiral liquid crystals.

A new series of chiral dopants, (R)-6,6'-halogenated (1b-1e, X = F, Cl, Br and I) and -methylated (1f) binaphthyl compounds, were designed and synthesized to create chiral liquid crystals by doping them into an achiral nematic liquid crystal (NLC). The influence of halogen (X = F, Cl, Br and I) and methyl substituent factors, such as steric, polar, and polarizability properties, on the helical twisting power (HTP) and their temperature dependences on the chiral dopants were investigated in two host NLCs with different characteristics, fluorinated JC-1041XX and N-(4-methoxybenzylidene)-4-butylaniline (MBBA). The chiral dopants possessing less steric and larger polarizability factors increased the HTP values. The structural similarity and electrostatic arene-arene interactions between the chiral dopants and the NLC molecules also exerted important influences on these values. The temperature dependence of the HTP (HTPt.d.) values also correlated well with the steric and polarizability substituents factors in the two host NLCs. Their correlation coefficients (R 2) depended on the molecular structural similarity between the chiral dopant and the NLC.

Reversible Broad-Spectrum Control of Selective Reflections of Chiral Nematic Phases by Closed-/Open-Type Axially Chiral Azo Dopants.

Invited for this month's cover picture is the groups of Professor Hirotsugu Kikuchi and Dr. Yasushi Okumura at the Institute for Materials Chemistry and Engineering at Kyushu University (Japan). External dynamic control of molecular self-organized superstructures with unique features has been researched, as these structures are applicable to chiral molecular devices. The cover picture shows photocontrol of selective reflection color that originated from the self-organized helical structure of chiral nematic liquid crystals (N*LCs) using closed-/open-type dopants. The drastic structure changes of the dopants by light stimuli enable reversible broad-spectrum control of selective reflections of N*LCs with opposite helical sign. Read the full text of the Full Paper at 10.1002/open.201700121.

Reversible Broad-Spectrum Control of Selective Reflections of Chiral Nematic Phases by Closed-/Open-Type Axially Chiral Azo Dopants.

We demonstrate reversible RGB-color photocontrol of a chiral nematic liquid crystal (N*LC) by using newly synthesized closed- and open-type chiral dopants. The photoswitching elements in the dopants are azobenzene units on axially chiral binaphthyl cores. Owing to cis-trans photoisomerization of the azobenzene units, both closed- and open-type compounds showed higher solubility, larger helical twisting power (HTP), and larger changes in HTP than conventional chiral dopants in host LCs. Thus, even at very low dopant concentrations, we successfully controlled the chirality of the induced helical structure of the N*LCs. Consequently, the N*LCs reflected right- and left-handed circularly polarized light (CPL) under a light stimulus. In the N*LCs with closed-type chiral dopants, the RGB-color reflection was reversibly controlled within several seconds. Interestingly, the open-type chiral dopant reversibly inverted CPL with opposite handedness in the near and short-wave IR regions. These novel materials are expected to realize new applications and perspectives in color information and similar technologies.

A Fluid Liquid-Crystal Material with Highly Polar Order.

An anomalously large dielectric permittivity of ≈104 is found in the mesophase temperature range (MP phase) wherein high fluidity is observed for a liquid-crystal compound having a 1,3-dioxane unit in the mesogenic core (DIO). In this temperature range, no sharp X-ray diffraction peak is observed at both small and wide Bragg angles, similar to that for a nematic phase; however, an inhomogeneous sandy texture or broken Schlieren one is observed via polarizing optical microscopy, unlike that for a conventional nematic phase. DIO exhibits polarization switching with a large polarization value, i.e., P = 4.4 µC cm-2 , and a parallelogram-shaped polarization-electric field hysteresis loop in the MP phase. The inhomogeneously aligned DIO in the absence of an electric field adopts a uniform orientation along an applied electric field when field-induced polarization switching occurs. Furthermore, sufficiently larger second-harmonic generation is observed for DIO in the MP phase. Second-harmonic-generation interferometry clearly shows that the sense of polarization is inverted when the +/- sign of the applied electric field in MP is reversed. These results suggest that a unidirectional, ferroelectric-like parallel polar arrangement of the molecules is generated along the director in the MP phase.