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Crystals
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State-of-the-Art Liquid Crystals Research in Japan
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State-of-the-Art Liquid Crystals Research in Japan

A special issue of Crystals (ISSN 2073-4352). This special issue belongs to the section "Liquid Crystals".

Deadline for manuscript submissions: closed (31 March 2023) | Viewed by 17634

Printed Edition Available!
A printed edition of this Special Issue is available here.

Special Issue Editors

Dr. Shigeyuki Yamada

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Guest Editor
Kyoto Institute of Technology, Faculty of Molecular Chemistry and Engineering, Kyoto, Japan
Interests: organic synthesis; fluorine; liquid crystals; fluorescence; phosphorescence; stimulus-responsive materials
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Kyosuke Isoda

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Guest Editor
Program in Advanced Materials Science, Faculty of Engineeering and Design, Kagawa University, Kagawa 760-0016, Japan
Interests: N-heteroacene; room-temperature liquid; stimuli-responsive liquid; liquid crystal; fluorescence
Prof. Dr. Takahiro Ichikawa

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Guest Editor
Department of Biotechnology, Tokyo University of Agriculture and Technology, Tokyo 183-8538, Japan
Interests: gyroid; liquid crystals; ionic liquids; bicontinuous cubic phase; ion conduction; polymer film
Dr. Kosuke Kaneko

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Guest Editor
Department of Applied Chemistry, College of Life Sciences, Ritsumeikan University, Kyoto 603-8577, Japan
Interests: liquid crystals; electrorheology; elastomer; siloxane
Special Issues, Collections and Topics in MDPI journals
Dr. Mizuho Kondo

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Department of Applied Chemistry, Graduate School of Engineering, University of Hyogo, Hyogo 651-2197, Japan
Interests: liquid crystals; fluorescence; mechanochromism; polymer
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Tsuneaki Sakurai

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Faculty of Molecular Chemistry and Engineering, Kyoto Institute of Technology, Kyoto 606-8585, Japan
Interests: liquid crystals; supramolecular chemistry; conjugated polymers; organic luminophores; organic semiconductors; nanomaterials
Prof. Dr. Atsushi Seki

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Guest Editor
Department of Chemistry, Graduate School of Science, Tokyo University of Science, Tokyo 162-8601, Japan
Interests: liquid-crystalline semiconductors; low-molecular-weight gelators; supramolecular ferroelectrics; stimuli-responsive materials
Prof. Dr. Mitsuo Hara

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Guest Editor
Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Aichi 464-8601, Japan
Interests: liquid crystalline polymer; organic-inorganic hybrid; surfactant; alignment control
Prof. Dr. Go Watanabe

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Guest Editor
Department of Science, Kitasato University, Tokyo 108-8641, Japan
Interests: liquid crystals; molecular dynamics simulation; biomolecules

Special Issue Information

Dear Colleagues,

Liquid crystals (LCs) are substances that have liquid properties (fluidity) and exhibits the optical anisotropy of crystals, and exhibits properties intermediate between crystals and liquids. LC molecules mainly consist of a rigid π structure and a flexible chain unit, which maintain some directional order (orientation), but do not have positional order. With a thermotropic or a lyotropic phase-transitions between crystal ⇄ LC ⇄ liquid, the molecular aggregates could be reversibly arranged and be expected by molecular dynamic simulations. The alteration of molecular aggregates is well known to significantly affect to various physical behavior, in the photophysical, optical, electrical, and chemical aspects. Therefore, there is no doubt that consolidating the results of cutting-edge liquid crystal research into a single special issue will greatly contribute to the future development of the fields of chemistry, materials, optics, and electronics.

This special issue, titled “State-of-the-Art Liquid Crystals Research in Japan” is intended to provide an innovative and broad perspective on the LC researches in Japan in the field of chemistry, physics, optics, photonics, photo-alignment techniques, material and devices, and others.

The potential topics include, but are not limited to:

  1. Exploration of novel LC materials
  2. Development of functional materials with LC characteristics
  3. Characterization of the structures for LC phases
  4. Exploration of simulation techniques for LC materials
  5. Applications using LC materials

Prof. Dr. Shigeyuki Yamada
Prof. Dr. Kyosuke Isoda
Prof. Dr. Takahiro Ichikawa
Prof. Dr. Kosuke Kaneko
Prof. Dr. Mizuho Kondo
Prof. Dr. Tsuneaki Sakurai
Prof. Dr. Atsushi Seki
Prof. Dr. Mitsuo Hara
Prof. Dr. Go Watanabe
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Crystals is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Liquid crystals
  • Blue-phase
  • Stimulus-responsive
  • Photoalignment control
  • Molecular dynamic simulations
  • Rheology
  • X-ray diffraction
  • Luminescence
  • Electrical conductivity

Related Special Issue

Published Papers (10 papers)

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Research

11 pages, 6967 KiB  
Article
Side-Chain Labeling Strategy for Forming Self-Sorted Columnar Liquid Crystals from Binary Discotic Systems
by Tsuneaki Sakurai, Kenichi Kato and Masaki Shimizu
Crystals 2023, 13(10), 1473; https://doi.org/10.3390/cryst13101473 - 10 Oct 2023
Viewed by 1252
Abstract
The spontaneous formation of self-sorted columnar structures of electron-donating and accepting π-conjugated molecules is attractive for photoconducting and photovoltaic properties. However, the simple mixing of donor–acceptor discotic molecules usually results in the formation of mixed-stacked or alternating-stacked columns. As a new strategy for [...] Read more.
The spontaneous formation of self-sorted columnar structures of electron-donating and accepting π-conjugated molecules is attractive for photoconducting and photovoltaic properties. However, the simple mixing of donor–acceptor discotic molecules usually results in the formation of mixed-stacked or alternating-stacked columns. As a new strategy for overcoming this problem, here, we report the “side-chain labeling” approach using binary discotic systems and realize the preferential formation of such self-sorted columnar structures in a thermodynamically stable phase. The demonstrated key strategy involves the use of hydrophobic and hydrophilic side chains. The prepared blend is composed of liquid crystalline phthalocyanine with branched alkyl chains (H2Pc) and perylenediimide (PDI) carrying alkyl chains at one side and triethyleneglycol (TEG) chains at the other side (PDIC12/TEG). To avoid the thermodynamically unfavorable contact among hydrophobic and hydrophilic chains, PDIC12/TEG self-assembles to stack up on top of each other and H2Pc as well, forming a homo-stacked pair of columns (self-sort). Importantly, H2Pc and PDIC12/TEG in the blend are macroscopically miscible and uniform, and mesoscopically segregated. The columnar liquid crystalline microdomains of H2Pc and PDIC12/TEG are homeotropically aligned in a glass sandwiched cell. The “labeling” strategy demonstrated here is potentially applicable to any binary discotic system and enables the preferential formation of self-sorted columnar structures. Full article
(This article belongs to the Special Issue State-of-the-Art Liquid Crystals Research in Japan)
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16 pages, 4776 KiB  
Article
Effects of Tetrafluorocyclohexa-1,3-Diene Ring Position on Photoluminescence and Liquid-Crystalline Properties of Tricyclic π-Conjugated Molecules
by Haruka Ohsato, Shigeyuki Yamada, Motohiro Yasui and Tsutomu Konno
Crystals 2023, 13(8), 1208; https://doi.org/10.3390/cryst13081208 - 03 Aug 2023
Viewed by 1539
Abstract
Tetrafluorocyclohexa-1,3-diene ring-containing tricyclic π-conjugated molecules are promising negative-dielectric-anisotropy guest species for vertical-alignment-type liquid-crystalline (LC) displays. Building on our previous work reporting the excellent photoluminescence (PL) properties of tricyclic π-conjugated molecules with central tetrafluorocyclohexa-1,3-diene rings, we herein synthesized four analogous molecules with terminal tetrafluorocyclohexa-1,3-diene [...] Read more.
Tetrafluorocyclohexa-1,3-diene ring-containing tricyclic π-conjugated molecules are promising negative-dielectric-anisotropy guest species for vertical-alignment-type liquid-crystalline (LC) displays. Building on our previous work reporting the excellent photoluminescence (PL) properties of tricyclic π-conjugated molecules with central tetrafluorocyclohexa-1,3-diene rings, we herein synthesized four analogous molecules with terminal tetrafluorocyclohexa-1,3-diene rings from commercially available precursors and investigated the effects of substituent type and diene ring position on PL and LC properties using microscopic and spectroscopic methods. One of the prepared molecules exhibited a relatively planar molecular structure and formed herringbone-type aggregates via π/F and CH/π interactions instead of forming stacked aggregates via π/π stacking interactions, thus exhibiting relatively strong PL in solution and crystalline states. Moreover, the PL color of this compound depended on the electronic character of its terminal substituents along the long molecular axis. Of the four prepared species, two featured terminal ethyl groups and formed one or more LC phases. The PL properties of these phases indicated that the related phase transition induced changes in the aggregate structure, PL wavelength, and PL color. Our results expand the applicability of CF2CF2 moiety-containing tricyclic compounds as functional molecules for the fabrication of next-generation PL, LC, and PL-LC materials. Full article
(This article belongs to the Special Issue State-of-the-Art Liquid Crystals Research in Japan)
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12 pages, 4796 KiB  
Article
Multichromic Behavior of Liquid Crystalline Composite Polymeric Films
by Mizuho Kondo, Satoka Yanai, Syouma Shirata, Takeshi Kakibe, Jun-ichi Nishida and Nobuhiro Kawatsuki
Crystals 2023, 13(5), 786; https://doi.org/10.3390/cryst13050786 - 09 May 2023
Viewed by 1211
Abstract
In this study, we describe the synthesis of a cholesterol-linked cyanostilobazole salt dye and the tuning of its luminescence by physical stimuli such as electricity and grinding. The dyes exhibited liquid-crystalline properties at temperatures above 170 °C. Some of the solutions were transformed [...] Read more.
In this study, we describe the synthesis of a cholesterol-linked cyanostilobazole salt dye and the tuning of its luminescence by physical stimuli such as electricity and grinding. The dyes exhibited liquid-crystalline properties at temperatures above 170 °C. Some of the solutions were transformed into orange luminescent gels upon the addition of poor solvents. When the solvent was evaporated, the resulting solid xerogel exhibited mechanochromism, its color changed, and its luminescent color changed from orange to red. Furthermore, we investigated the construction of functional gels (mechanochromic gels) that can respond to two stimuli, damage detection by abrasive responsiveness, and electrical response using ionic liquid complexes of polymers as dispersing media. This study provides a new strategy for tuning and switching luminescence using non-chemical stimuli in a single-component system using aggregation. Full article
(This article belongs to the Special Issue State-of-the-Art Liquid Crystals Research in Japan)
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10 pages, 3584 KiB  
Communication
Angular Dependence of Guest–Host Liquid Crystal Devices with High Pretilt Angle Using Mixture of Vertical and Horizontal Alignment Materials
by Masahiro Ito, Eriko Fukuda, Mitsuhiro Akimoto, Hikaru Hoketsu, Yukitaka Nakazono, Haruki Tohriyama and Kohki Takatoh
Crystals 2023, 13(4), 696; https://doi.org/10.3390/cryst13040696 - 19 Apr 2023
Cited by 1 | Viewed by 1164
Abstract
To date, devices exhibiting incidence-angle-dependent transmittance have been fabricated by imparting an angle to a bulk liquid crystal (LC) by aligning the LC in the vicinity of one substrate horizontally (with respect to the substrate) while aligning the LC in the vicinity of [...] Read more.
To date, devices exhibiting incidence-angle-dependent transmittance have been fabricated by imparting an angle to a bulk liquid crystal (LC) by aligning the LC in the vicinity of one substrate horizontally (with respect to the substrate) while aligning the LC in the vicinity of another substrate vertically. Another approach has been to control LC angles near substrates by blending or layering horizontal and vertical alignment films. In this study, we control LC angles near substrates by controlling the pretilt angles of blended alignment films; for specific angles, we use dichroic dyes to characterize the incidence angle dependence of these LC devices. Using a guest/host LC device with a pretilt angle near 45°, we successfully construct an LC element with a transmittance peak near a polar angle of 45°. Full article
(This article belongs to the Special Issue State-of-the-Art Liquid Crystals Research in Japan)
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Graphical abstract

11 pages, 3173 KiB  
Article
Photoalignment and Photofixation of Chromonic Mesophase in Ionic Linear Polysiloxanes Using a Dual Irradiation System
by Mitsuo Hara, Ayaka Masuda, Shusaku Nagano and Takahiro Seki
Crystals 2023, 13(2), 326; https://doi.org/10.3390/cryst13020326 - 15 Feb 2023
Cited by 1 | Viewed by 1900
Abstract
Photoalignment technology enables macroscopic alignment of liquid crystalline molecules and their aggregates in a non-contact process by irradiating photo-responsive liquid crystalline compounds with linearly polarized light. Because photoalignment techniques prevent dust generation and uneven stretching, and accomplish fine and complex patterning, they are [...] Read more.
Photoalignment technology enables macroscopic alignment of liquid crystalline molecules and their aggregates in a non-contact process by irradiating photo-responsive liquid crystalline compounds with linearly polarized light. Because photoalignment techniques prevent dust generation and uneven stretching, and accomplish fine and complex patterning, they are involved in the practical process of fabricating display panels, and continue to be applied in the research and creation of various anisotropic materials. Brilliant yellow (BY), a chromonic liquid crystal, has attracted considerable attention as the photoalignment sublayer in recent years, because of its ability to induce a high dichroic nature among many photo-responsive liquid crystalline materials. However, its dichroism is not maintained after prolonged exposure to a humid environment because of its intrinsic strong hygroscopicity of ionic BY molecules. In this study, to overcome this drawback, the photoalignment and successive photo-fixation of the BY columnar phase is proposed using UV-curable ionic polysiloxane as a matrix. Visible light was used for the photoalignment of the BY columnar phase, and UV light for photo-fixation. Consequently, the columnar chromonic phase is found to retain its orientation even after 4 h of exposure to a highly humid environment. Full article
(This article belongs to the Special Issue State-of-the-Art Liquid Crystals Research in Japan)
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13 pages, 3648 KiB  
Article
Development of Hydrogen-Bonded Dimer-Type Photoluminescent Liquid Crystals of Fluorinated Tolanecarboxylic Acid
by Shigeyuki Yamada, Mitsuki Kataoka, Keigo Yoshida, Masakazu Nagata, Tomohiro Agou, Hiroki Fukumoto and Tsutomu Konno
Crystals 2023, 13(1), 25; https://doi.org/10.3390/cryst13010025 - 23 Dec 2022
Cited by 5 | Viewed by 1643
Abstract
Functional molecules possessing photoluminescence (PL) and liquid-crystalline (LC) behaviors, known as photoluminescent liquid crystals, along with a small molecular structure, have attracted significant attention. Fluorinated tolane skeletons are small π-conjugated structures, which are promising candidates for such functional molecules. These structures were revealed [...] Read more.
Functional molecules possessing photoluminescence (PL) and liquid-crystalline (LC) behaviors, known as photoluminescent liquid crystals, along with a small molecular structure, have attracted significant attention. Fluorinated tolane skeletons are small π-conjugated structures, which are promising candidates for such functional molecules. These structures were revealed to exhibit strong PL in solid state but no LC behavior. Based on a report on hydrogen-bonded dimer-type LC molecules of carboxylic acid, in this study, we designed and synthesized a series of fluorinated tolanecarboxylic acids (2,3,5,6-tetrafluoro-4-[2-(4-alkoxyphenyl)ethyn-1-yl]benzoic acids) as promising PLLC molecules. Evaluation of the LC behavior revealed that fluorinated tolanecarboxylic acids with a longer alkoxy chain than a butoxy chain exhibited nematic LC behavior. Additionally, fluorinated tolanecarboxylic acids showed intense PL in the solution and crystalline states. Notably, fluorinated tolanecarboxylic acid with an aggregated structure in the nematic LC phase also exhibited PL with a slight blue shift in PL maximum wavelength compared to the crystalline state. The present fluorinated tolanecarboxylic acid exhibiting PL and LC characteristics in a single molecule can be applied to thermoresponsive PL materials, such as a PL thermosensor. Full article
(This article belongs to the Special Issue State-of-the-Art Liquid Crystals Research in Japan)
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12 pages, 8028 KiB  
Article
Twist–Bend Nematic Phase Behavior of Cyanobiphenyl-Based Dimers with Propane, Ethoxy, and Ethylthio Spacers
by Yuki Arakawa, Yuto Arai, Kyohei Horita, Kenta Komatsu and Hideto Tsuji
Crystals 2022, 12(12), 1734; https://doi.org/10.3390/cryst12121734 - 01 Dec 2022
Cited by 6 | Viewed by 1644
Abstract
The twist–bend nematic (NTB) phase is a liquid crystal (LC) phase with a heliconical structure that typically forms below the temperature of the conventional nematic (N) phase. By contrast, the direct transition between the NTB and isotropic (Iso) phases without [...] Read more.
The twist–bend nematic (NTB) phase is a liquid crystal (LC) phase with a heliconical structure that typically forms below the temperature of the conventional nematic (N) phase. By contrast, the direct transition between the NTB and isotropic (Iso) phases without the intermediation of the N phase rarely occurs. Herein, we demonstrate the effects of linkage type (i.e., methylene, ether, and thioether) on the typical Iso–N–NTB and rare direct Iso–NTB phase-transition behaviors of cyanobiphenyl (CB) dimers CB3CB, CB2OCB, and CB2SCB bearing three-atom-based propane, ethoxy, and ethylthio spacers, respectively. In our previous study, CB2SCB exhibited the monotropic direct Iso–NTB phase transition. In this study, we report that CB3CB also shows the direct Iso–NTB phase transition, whereas CB2OCB exhibits the typical Iso–N–NTB phase sequence with decreasing temperature. The Iso–LC (Iso–NTB or Iso–N) phase-transition temperatures upon cooling show the order CB2OCB (108 °C) > CB3CB (49 °C) > CB2SCB (43 °C). The thioether-linked CB2SCB is vitrifiable, whereas CB3CB and CB2OCB exhibit strong crystallization tendencies. The phase-transition behaviors are also discussed in terms of the three bent homologous series with different oligomethylene spacers n: CBnCB, CBnOCB, and CBnSCB. Full article
(This article belongs to the Special Issue State-of-the-Art Liquid Crystals Research in Japan)
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11 pages, 5025 KiB  
Article
Chromonic Ionic Liquid Crystals Forming Nematic and Hexagonal Columnar Phases
by Takahiro Ichikawa, Mei Kuwana and Kaori Suda
Crystals 2022, 12(11), 1548; https://doi.org/10.3390/cryst12111548 - 29 Oct 2022
Cited by 2 | Viewed by 1475
Abstract
We designed an ionic salt by combining a π-conjugated anion and a cholinium cation. It formed homogeneous mixtures with water in various weight ratios. The obtained mixtures showed chromonic liquid-crystalline behavior in a wider concentration range as compared to analogous compounds with inorganic [...] Read more.
We designed an ionic salt by combining a π-conjugated anion and a cholinium cation. It formed homogeneous mixtures with water in various weight ratios. The obtained mixtures showed chromonic liquid-crystalline behavior in a wider concentration range as compared to analogous compounds with inorganic cations. Although only an exhibition of nematic phases was previously reported by Kasianova et al. for analogous compounds with an inorganic cation in 2010, the ionic salt with a cholinium cation showed not only nematic phases but also hexagonal columnar phases. The formation of hexagonal columnar phases is attributed to its ability to form mesophases even in a high concentration range, which enables the cylindrical aggregates of the π-conjugated anions to form dense packing. By examining the states of the water molecules, we revealed that the ability of the cholinium cation to form a hydrated ionic liquid state strongly contributes to the widening of the concentration range forming chromonic liquid-crystalline behavior. Full article
(This article belongs to the Special Issue State-of-the-Art Liquid Crystals Research in Japan)
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15 pages, 8307 KiB  
Article
Chiral π-Conjugated Liquid Crystals: Impacts of Ethynyl Linker and Bilateral Symmetry on the Molecular Packing and Functions
by Atsushi Seki, Kazuki Shimizu and Ken’ichi Aoki
Crystals 2022, 12(9), 1278; https://doi.org/10.3390/cryst12091278 - 09 Sep 2022
Cited by 1 | Viewed by 2146
Abstract
Recently, various chiral aromatic compounds, including chiral π-conjugated liquid crystals, have been developed for their unique photofunctions. One of the typical photofunctions is the bulk photovoltaic effect of ferroelectric π-conjugated liquid crystals, which integrates a polar environment based on molecular chirality with an [...] Read more.
Recently, various chiral aromatic compounds, including chiral π-conjugated liquid crystals, have been developed for their unique photofunctions. One of the typical photofunctions is the bulk photovoltaic effect of ferroelectric π-conjugated liquid crystals, which integrates a polar environment based on molecular chirality with an extended π-conjugation system. Tuning the spectral properties and molecular packing is essential for improving the optical functions of the chiral π-conjugated liquid crystals. Herein, we examined the effects of an ethynyl linker and bilateral symmetry on the liquid-crystalline (LC) properties and π-conjugated system through detailed characterization via polarizing optical microscopy, differential scanning calorimetry, and X-ray diffraction analysis. The spreading of the π-conjugated system was evaluated using UV–vis absorption and photoluminescence spectroscopy. Bilateral symmetry affects the LC and photoluminescent properties. Hetero-substitution with a sparse ethynyl linker likely allows the formation of an interdigitated smectic LC structure. Because the molecular packing and photophysical properties can affect the photo- and electrical functions, we believe this study can promote the molecular design of novel functional π-conjugated materials, such as chiral ferroelectric π-conjugated liquid crystals, exhibiting the bulk photovoltaic effect. Full article
(This article belongs to the Special Issue State-of-the-Art Liquid Crystals Research in Japan)
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10 pages, 1983 KiB  
Article
Luminescent Behavior of Liquid–Crystalline Gold(I) Complexes Bearing a Carbazole Moiety: Effects of Substituent Bulkiness
by Kumar Siddhant, Ganesan Prabusankar and Osamu Tsutsumi
Crystals 2022, 12(6), 810; https://doi.org/10.3390/cryst12060810 - 08 Jun 2022
Viewed by 2196
Abstract
Organometallic materials that exhibit white luminescence in condensed phases are of considerable interest for lighting and display applications. Herein, new carbazole-based Au(I) complexes containing an isocyanide group and a long pentyl chain were synthesized. The complex with an unsubstituted carbazole moiety exhibited a [...] Read more.
Organometallic materials that exhibit white luminescence in condensed phases are of considerable interest for lighting and display applications. Herein, new carbazole-based Au(I) complexes containing an isocyanide group and a long pentyl chain were synthesized. The complex with an unsubstituted carbazole moiety exhibited a white emission at room temperature as well as nematic liquid crystalline behavior. Color tunability from white to blue was achieved when bulkier substituents were introduced at the 3 and 6 positions of the carbazole moiety. Furthermore, all complexes possessed long phosphorescence lifetimes in the crystal state. The proposed design framework provides new opportunities for practical applications using luminescent organometallic molecules. Full article
(This article belongs to the Special Issue State-of-the-Art Liquid Crystals Research in Japan)
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