Multi-Color Photoluminescence Based on Mechanically and Thermally Induced Liquid-Crystalline Phase Transitions of a Hydrogen-Bonded Benzodithiophene Derivative.

Controlling assembled structures of π-conjugated liquid-crystalline molecules is of great interest in the development of stimuli-responsive luminescent materials due to their molecular motility in the ordered states. Herein, we describe a mechanoresponsive hydrogen-bonded benzodithiophene liquid-crystalline molecule that exhibits a tricolor photoluminescence switching at ambient temperature. The compound shows a shear-induced phase transition from a rectangular columnar to a metastable optically anisotropic mesophase, which is accompanied by the luminescent color change from yellow to sky-blue. The metastable mesophase exhibits a time-responsive transformation to another metastable mesophase showing a blue-green emission through isothermal aging at room temperature. The luminescent color of aged sample reverts back to the initial yellow color by thermal annealing at 150 °C. These dynamic structural changes accompanied by the emission color changes are governed by distinct π-stacking modes and hydrogen-bonded patterns. The shear-induced luminescent color change from yellow to blue is found to occur above the shear strain of 390 % at which the shear stress is 2.4×105  Pa as determined from dynamic viscoelastic measurements.

Self-Assembly of Giant Spherical Liquid-Crystalline Complexes and Formation of Nanostructured Dynamic Gels that Exhibit Self-Healing Properties.

Supramolecular self-assembly of 24 forklike mesogenic ligands and 12 transition metal ions led to the formation of giant spherical coordination complexes that exhibit liquid-crystalline (LC) phases. Self-healing LC supramolecular gels were also obtained through the introduction of these LC nanostructured supramolecular giant spherical complexes into dynamic covalent networks formed by cross-linkers and bifunctional polymers. The giant spherical structures of the PdII complexes with 72 rodlike moieties on the periphery were characterized by NMR, diffusion-ordered NMR spectroscopy, and mass spectrometry. These complexes are stable and exhibit lyotropic LC behavior, while the mesogenic ligands show thermotropic LC properties. The self-assembled LC structures of the spherical complexes can be tuned by the length of the rodlike moieties.

Self-Assembled Fibers Containing Stable Organic Radical Moieties: Alignment and Magnetic Properties in Liquid Crystals.

Macroscopically oriented stable organic radicals have been obtained by using a liquid-crystalline (LC) gel composed of an l-isoleucine-based low molecular weight gelator containing a 2,2,6,6-tetramethylpiperidine 1-oxyl moiety. The LC gel has allowed magnetic measurements of the oriented organic radical. The gelator has formed fibrous aggregates in liquid crystals via intermolecular hydrogen bonds. The fibrous aggregates of the radical gelator are formed and oriented on cooling by applying a magnetic field to the mixture of liquid crystals and the gelator. Superconducting quantum interference device (SQUID) measurements have revealed that both oriented and nonoriented fibrous aggregates exhibited antiferromagnetic interactions, in which super-exchange interaction constant J is estimated as -0.89 cm(-1) .

Ionic Switch Induced by a Rectangular-Hexagonal Phase Transition in Benzenammonium Columnar Liquid Crystals.

We demonstrate switching of ionic conductivities in wedge-shaped liquid-crystalline (LC) ammonium salts. A thermoreversible phase transition between the rectangular columnar (Colr) and hexagonal columnar (Colh) phases is used for the switch. The ionic conductivities in the Colh phase are about four orders of magnitude higher than those in the Colr phase. The switching behavior of conductivity can be ascribed to the structural change of assembled ionic channels. X-ray experiments reveal a highly ordered packing of the ions in the Colr phase, which prevents the ion transport.

A planarized triphenylborane mesogen: discotic liquid crystals with ambipolar charge-carrier transport properties.

A discotic liquid-crystalline (LC) material, consisting of a planarized triphenylborane mesogen, was synthesized. X-ray diffraction analysis confirmed that this compound forms a hexagonal columnar LC phase with an interfacial distance of 3.57 Šbetween the discs. At ambient temperature, this boron-centered discotic liquid crystal exhibited ambipolar carrier transport properties with electron and hole mobility values of approximately 10(-3) and 3×10(-5)  cm(2) V(-1) s(-1), respectively.

Macroscopic photocontrol of ion-transporting pathways of a nanostructured imidazolium-based photoresponsive liquid crystal.

The photocontrol of the macroscopic alignment of nanostructured 2D ion-transporting pathways is described. The uniplanar homogeneous alignment of the thermotropic smectic (Sm) liquid-crystalline (LC) phase has been successfully achieved via photoinduced reorientation of the azobenzene groups of the imidazolium-based LC material. The ionic layers of the Sm LC phase are macroscopically oriented perpendicular to the surface of the glass substrate. The oriented films show anisotropic ion conduction in the Sm phase. This is the first example of the macroscopic photoalignment of ion-conductive LC arrays. Reversible switching of homeotropic and homogeneous alignments has also been achieved for the LC material. These materials and the alignment methodology may be useful in the development of ion-based circuits and memory devices.

Ionic Liquid Crystal-Polymer Composite Electromechanical Actuators: Design of Two-Dimensional Molecular Assemblies for Efficient Ion Transport and Effect of Electrodes on Actuator Performance.

We present the development of free-standing ionic liquid crystal-polymer composite electrolyte films aimed at achieving high-frequency response electromechanical actuators. Our approach entails designing novel layered ionic liquid-crystalline (LC) assemblies by complexing a mesomorphic dimethylphosphate with either a lithium salt or a room-temperature ionic liquid through the formation of ion-dipole interactions or hydrogen bonds. These electrolytes, exhibiting room-temperature ionic conductivities on the order of 10-4 S cm-1 and wide LC temperature ranges up to 77 °C, were successfully integrated into porous polymer networks. We systematically investigated the impact of ions and electrodes on the performance of ionic electroactive actuators. Specifically, the Li+-based liquid crystal-polymer composite actuator with PEDOT:PSS electrodes demonstrated the highest bending deformation, achieving a strain of 0.68% and exhibiting a broad frequency response up to 110 Hz, with a peak-to-peak displacement of 3 µm. In contrast, the ionic-liquid-based liquid crystal-polymer composite actuator with active carbon electrodes showcased a bending response at a maximum frequency of 50 Hz and a force generation of 0.48 mN, without exhibiting the back relaxation phenomenon. These findings offer valuable insights for advancing high-performance electromechanical systems with applications ranging from soft robotics to haptic interfaces.

3D Anhydrous proton-transporting nanochannels formed by self-assembly of liquid crystals composed of a sulfobetaine and a sulfonic acid.

Herein we describe anhydrous proton transportation through 3D interconnected pathways formed by self-assembled molecular complexes. A thermotropic bicontinuous cubic (Cub(bi)) phase has been successfully obtained by mixing a wedge-shaped sulfobetaine with benzenesulfonic acid in different ratios. These ionic complexes exhibit the Cub(bi) phase in a wide range of temperatures, while the single zwitterionic compound shows only a columnar hexagonal phase, and benzenesulfonic acid is nonmesomorphic. Anhydrous proton conduction on the order of 10(-4) S cm(-1) has been achieved for the mixture in the Cub(bi) phase over 100 °C, which can be useful for the development of new electrolytes for the next generation of fuel cells.

Highly luminescent and photoconductive columnar liquid crystals with a thiophene-oxadiazole backbone.

We report columnar liquid-crystalline thiophene-oxadiazole molecules, which can be oriented by electric field and exhibit photodiode properties with an open-circuit voltage of 1 V. Their yellow luminescence can be excited by UV-visible or infrared light. Their room-temperature phosphorescence turns brighter upon heating.

Photocured Liquid-Crystalline Polymer Electrolytes with 3D Ion Transport Pathways for Electromechanical Actuators.

Self-assembly of ionic molecules into hierarchical ordered structures is a promising route to new types of solid electrolytes with enhanced ion transport. Herein, we report a liquid-crystalline polymer electrolyte membrane that contains three-dimensionally (3D) interconnected ionic pathways. To build this membrane, we used wedge-shaped amphiphilic molecules that have two ionic heads and a lipophilic tail. These molecules were combined with a low content of ionic liquid (5.6 wt %) to form a hexagonal columnar phase, where the self-assembled lipophilic cylinders were surrounded by the ionic shell. Photopolymerization of this phase produced flexible nanostructured films with 3D ionic pathways, which can serve as an electrolyte layer in soft robotic actuators. Ionic transport in the 3D pathways leads to shape memory capability as well as durable bending actuation with a voltage-controllable blocking force. Furthermore, we find a significant enhancement of actuation for the nanostructured electrolyte compared with the corresponding amorphous electrolyte.

Induction of thermotropic bicontinuous cubic phases in liquid-crystalline ammonium and phosphonium salts.

Two series of wedge-shaped onium salts, one ammonium and the other phosphonium, having 3,4,5-tris(alkyloxy)benzyl moieties, exhibit thermotropic bicontinuous "gyroid" cubic (Cub(bi)) and hexagonal columnar liquid-crystalline (LC) phases by nanosegregation between ionophilic and ionophobic parts. The alkyl chain lengths on the cationic moieties, anion species, and alkyl chain lengths on the benzyl moieties have crucial effects on their thermotropic phase behavior. For example, triethyl-[3,4,5-tris(dodecyloxy)benzyl]ammonium hexafluorophosphate forms the thermotropic Ia3d Cub(bi) LC phase, whereas an analogous compound with trifluoromethanesulfonate anion shows no LC properties. Synchrotron small-angle diffraction intensities from the Ia3d Cub(bi) LC materials provide electron density maps in the bulk state. The resulting maps show convincingly that the Ia3d Cub(bi) structure is composed of three-dimensionally interconnected ion nanochannel networks surrounded by aliphatic domains. A novel differential mapping technique has been applied successfully. The map of triethyl-[3,4,5-tris(decyloxy)benzyl]ammonium tetrafluoroborate has been subtracted from that of the analogous ammonium salt with hexafluorophosphate anion in the Ia3d Cub(bi) phases. The differential map shows that the counteranions are located in the core of the three-dimensionally interconnected nanochannel networks. Changing from trimethyl- via triethyl- to tripropylammonium cation changes the phase from columnar to Cub(bi) to no mesophase, respectively. This sensitivity to the widened shape for the narrow end of the molecule is explained successfully by the previously proposed semiquantitative geometric model based on the radial distribution of volume in wedge-shaped molecules. The LC onium salts dissolve lithium tetrafluoroborate without losing the Ia3d Cub(bi) LC phase. The Cub(bi) LC materials exhibit efficient ion-transporting behavior as a result of their 3D interconnected ion nanochannel networks. The Ia3d Cub(bi) LC material formed by triethyl-[3,4,5-tris(decyloxy)benzyl]phosphonium tetrafluoroborate shows ionic conductivities higher than the analogous Ia3d Cub(bi) material based on ammonium salts. The present study indicates great potential of Cub(bi) LC nanostructures consisting of ionic molecules for development of transportation nanochannel materials.

Room-Temperature Zwitterionic Liquid Crystals for Mechanical Actuators.

We have developed room-temperature smectic liquid-crystalline (LC) ion conductors by the self-assembly of a zwitterionic mesogenic compound and a series of fluorinated lithium salts. The conductivity of lithium bis(trifluoromethylsulfonyl)imide LC complex reached 4 × 10-3 S cm-1 at ambient conditions. This LC complex sandwiched between two conductive polymer electrodes can be used in low-voltage mechanical actuators with a peak-to-peak bending deflection of ca. 20 mm upon ±1 V, 0.03 Hz excitation.

Electroactive Soft Actuators Based on Columnar Ionic Liquid Crystal/Polymer Composite Membrane Electrolytes Forming 3D Continuous Ionic Channels.

Here, we report low-voltage-driven fast-response nanostructured columnar ionic liquid crystal/polymer composite actuators that form three-dimensional continuous ion channels. A three-component self-assembly of a zwitterionic rod-like molecule (49.5 wt %), an ionic liquid (27.5 wt %), and poly(vinyl alcohol) (23.0 wt %) provided a free-standing stretchable membrane electrolyte. The dissociated ions can move through a continuous 3D ionophilic matrix surrounding the hydrophobic columns formed by the hexagonally organized rod-mesogens. Three-layer actuators composed of the electrolyte film sandwiched between two conductive polymer film electrodes of doped polythiophene exhibited a bending motion with 0.32% strain and moved 2 mm within 220 ms under 1 V at 0.1 Hz in 70% relative humidity due to the formation of electric double layers at the soft solid electrolyte/electrode interfaces. The bending strain of the columnar nanostructured actuator is comparable to those of polymer iongel actuators and block polymer actuators containing 25-80 wt % of ionic liquids. It is noteworthy that a small number of ions organized into the 3D nanochannels can generate the large bending deformation, which can contribute to reduce the risk of leakage of ions and the production cost. In addition, we have demonstrated a low-voltage-driven deformable mirror actuator that is expected to be applied to optical devices.

Oxidation-degree-dependent moisture-induced actuation of a graphene oxide film.

Multilayered films prepared from graphene oxide (GO) subjected to a single oxidation process (1GO) can actuate in response to moisture, whereas those prepared from GO subjected to two oxidation processes (2GO) lose this ability. To elucidate the origin of this difference, the structures and properties of various multilayered films and their contents were analyzed. According to atomic force microscopy images, the lateral size of the GO monolayer in 2GO (2.0 ± 0.4 µm) was smaller than that in 1GO (3.2 ± 0.4 µm), although this size difference did not affect actuation. Scanning electron microscopy images of the cross sections of both films showed fine multilayered structures and X-ray diffraction measurements showed the moisture sensitive reversible change in the interlayer distances for both films. Both films adsorbed 30 wt% moisture in 60 s with different water contents at the bottom moist sides and top air sides of the films. Nanoindentation experiments showed hardness values (1GO: 156 ± 67 MPa; 2GO: 189 ± 97 MPa) and elastic modulus values (1GO: 4.7 ± 1.7 GPa; 2GO: 5.8 ± 3.2 GPa) typical of GO, with no substantial difference between the films. On the contrary, the 1GO film bent when subjected to a weight equal to its own weight, whereas the 2GO film did not. Such differences in the macroscopic hardness of GO films can affect their moisture-induced actuation ability.

3D interconnected ionic nano-channels formed in polymer films: self-organization and polymerization of thermotropic bicontinuous cubic liquid crystals.

Thermotropic bicontinuous cubic (Cub(bi)) liquid-crystalline (LC) compounds based on a polymerizable ammonium moiety complexed with a lithium salt have been designed to obtain lithium ion-conductive all solid polymeric films having 3D interconnected ionic channels. The monomer shows a Cub(bi) phase from -5 to 19 °C on heating. The complexes retain the ability to form the Cub(bi) LC phase. They also form hexagonal columnar (Col(h)) LC phases at temperatures higher than those of the Cub(bi) phases. The complex of the monomer and LiBF(4) at the molar ratio of 4:1 exhibits the Cub(bi) and Col(h) phases between -6 to 19 °C and 19 to 56 °C, respectively, on heating. The Cub(bi) LC structure formed by the complex has been successfully preserved by in situ photopolymerization through UV irradiation in the presence of a photoinitiator. The resultant nanostructured film is optically transparent and free-standing. The X-ray analysis of the film confirms the preservation of the self-assembled nanostructure. The polymer film with the Cub(bi) LC nanostructure exhibits higher ionic conductivities than the polymer films obtained by photopolymerization of the complex in the Col(h) and isotropic phases. It is found that the 3D interconnected ionic channels derived from the Cub(bi) phase function as efficient ion-conductive pathways.

Self-healing and shape memory functions exhibited by supramolecular liquid-crystalline networks formed by combination of hydrogen bonding interactions and coordination bonding.

We here report a new approach to develop self-healing shape memory supramolecular liquid-crystalline (LC) networks through self-assembly of molecular building blocks via combination of hydrogen bonding and coordination bonding. We have designed and synthesized supramolecular LC polymers and networks based on the complexation of a forklike mesogenic ligand with Ag+ ions and carboxylic acids. Unidirectionally aligned fibers and free-standing films forming layered LC nanostructures have been obtained for the supramolecular LC networks. We have found that hybrid supramolecular LC networks formed through metal-ligand interactions and hydrogen bonding exhibit both self-healing properties and shape memory functions, while hydrogen-bonded LC networks only show self-healing properties. The combination of hydrogen bonds and metal-ligand interactions allows the tuning of intermolecular interactions and self-assembled structures, leading to the formation of the dynamic supramolecular LC materials. The new material design presented here has potential for the development of smart LC materials and functional LC membranes with tunable responsiveness.

m x n stacks of discrete aromatic stacks in solution.

Septuple columnar stacks of large aromatic molecules with solubilizing side chains have been synthesized via one-step multicomponent self-assembly. At increased concentrations in aqueous solution, m x n aggregates of aromatic stacks form. The simple addition of water induces lyotropic liquid-crystalline mesophases.

Ferroelectric Liquid-Crystalline Binary Mixtures Based on Achiral and Chiral Trifluoromethylphenylterthiophenes.

This paper presents a new family of ferroelectric smectic liquid-crystalline binary mixtures composed of achiral and chiral trifluoromethylphenylterthiophenes. The chiral symmetry breaking of the ferroelectric smectic phases can lead to chiral photovoltaic (CPV) effects, as a type of ferroelectric photovoltaic (FePV) effect, which is caused by the internal electric field originating from the spontaneous polarization. These ferroelectric properties were examined using the Sawyer-Tower method, and the CPV effect was confirmed by measuring the steady-state photocurrent response under zero bias. We found that the remnant polarization and photocurrent density in the polarized ferroelectric phases increased nonlinearly with the increase in the content of the chiral component in the mixture. Moreover, the hole mobility evaluated by time-of-flight measurements was kept constant by varying the composition. More than 40 mol % of the chiral component was required to form the polar structure, inducing the CPV effect. Binary mixture systems are advantageous for not only optimizing liquid crystal structures and temperature ranges but also facilitating the design of materials exhibiting CPV effects.

Electric field-assisted alignment of self-assembled fibers composed of hydrogen-bonded molecules having laterally fluorinated mesogens.

Aligned fibrous aggregates of amide compounds having laterally fluorinated aromatic mesogens have been successfully obtained by the application of the alternating current electric field (1.0 V/microm, 1 kHz) in dodecylbenzene. In contrast, randomly entangled fibers are formed in the solvent without electric fields. For the analogous compounds without fluorine substituent, no aligned fibrous aggregates have been obtained under the electric fields. The electric field alignment of the fibers should be assisted by the fluorinated rod-shaped mesogens that exhibit negative dielectric anisotropy.

Self-assembly of functional columnar liquid crystals.

Columnar liquid crystals have recently been developed as dynamically functional anisotropic materials. In this feature article, some recent examples of the materials design and functionalisation of columnar liquid crystals are described. Not only disklike molecules but also molecules with unconventional shapes can form columnar liquid-crystalline assemblies with nanosegregated structures. Moreover use of non-covalent interactions such as hydrogen bonding, ionic and electron donor-acceptor interactions leads to the formation of supramolecular functional columnar materials that are stimuli-responsive. Nanosegregated columnar molecular order can also be used for one-dimensional transportation of electrons, ion and molecules.