Sunlight-Driven Smart Windows with a Wide Temperature Range of Optical Switching Based on Chiral Nematic Liquid Crystals.

Photoresponsive liquid crystals are promising materials for sunlight-driven smart windows, which can automatically change their optical states in response to sunlight and control energy flow between the inside and outside of a building. Herein, liquid-crystalline systems are developed that show a transparent-scattering transition upon irradiation with sunlight in a wide temperature range. Push-pull azobenzenes with axial chirality have been newly developed as photochromic chiral dopants to allow changes in mesostructures of liquid crystals in response to sunlight. To realize optical switching, photochromic and photoinert chiral compounds with opposite handedness of helical twisting are doped in liquid crystals. This liquid crystalline sample with a compensated nematic phase is transparent in its initial state. Upon irradiation with sunlight, this sample transforms to a scattering state due to the formation of helical mesostructures along with photoisomerization of azobenzene moieties and the change in the helical twisting power. After the cease of irradiation, the sample reverts to the transparent state through thermal back isomerization of azobenzene moieties. This system significantly improves the operating temperature range of sunlight-driven smart windows based on liquid crystals: the transparent-scattering transition is observed at 4-42 °C. The present mechanism allows development of autonomous and wireless smart windows adaptable to various environments.

Inducing Motions of Polymers in Liquid Nitrogen with Light.

Polymer materials that show macroscopic deformation in response to external stimuli are feasible for novel soft actuators including microactuators. Incorporation of photochromic moieties, such as azobenzenes, into polymer networks enables macroscopic deformation under irradiation with light through photoisomerization. Under cryogenic conditions, however, it has been difficult to induce macroscopic deformation as polymers lose their soft nature due to the severe restrictions of molecular motions. Here, activation of molecular motions and macroscopic deformation in liquid nitrogen only with light for polymers containing photochromic moieties is reported. Photoinduced bending of polymer networks with normal azobenzenes in liquid nitrogen is enabled by preliminary UV irradiation at room temperature to produce cis-isomers. To realize photoinduced deformation directly in liquid nitrogen, polymer networks are functionalized with bridged azobenzenes, which exist as cis-isomers in thermodynamic equilibrium. The films with bridged azobenzenes exhibit reversible photoisomerization and bending upon irradiation with light in liquid nitrogen without the need of preliminary irradiation, implying that the change in conformation of polymer chains can be isothermally induced even under cryogenic conditions. Achievement of flexible motions under cryogenic conditions through isothermal processes will greatly expand the operating temperature range of soft actuators.

Janus Photochemical/Photothermal Azobenzene Inverse Opal Actuator with Shape Self-Recovery toward Sophisticated Motion.

Azobenzene actuators have aroused enormous research interest due to their excellent performance and promising applications in the fields of soft robots, artificial muscles, etc. However, there are still challenges for the fabrication of azobenzene actuators with a sophisticated actuation mode owing to the unitary actuation direction and slow thermal relaxation of cis- to trans-azobenzene mesogens. To solve these problems, this paper presents a facile fabrication method of a Janus azobenzene inverse opal actuator with one side made of the monodomain azobenzene polymer and the other side made of the polydomain azobenzene inverse opal structure. Gradient-layer spacing structure of the film in its cross section is proven by synchrotron small-angle X-ray diffraction. The introduction of the inverse opal structure mainly provides a polydomain mesogen alignment, large specific surface area, low elastic modulus, and structure color. The synergetic actuation of the photochemical/photothermal mode produces multiple actuation directions, a larger actuation force, and an alteration of the structure color. Shape self-recovery of this Janus azobenzene actuator contributes to some promising applications, such as crawling on a smooth surface, driving an engine axis, and logic electric circuit for the coding technique. This work is of great significance for the design and fabrication of novel-type photoactuators.

Single-, Dual-, Triple, and Quadruple-Wavelength Surface-Emitting Lasing in Blue-Phase Liquid Crystal.

Soft organic lasers with multiwavelength output and high spectral purity are of crucial importance for versatile photonic devices, owing to their monochromaticity, coherence, and high intensity. However, there remain challenges for the achievement of surface-emitting multiwavelength lasing in soft photonic crystals, and the relative mechanisms need to be investigated. Herein, single-, dual-, triple-, and quadruple-wavelength lasers are successfully achieved in dye-doped blue-phase liquid crystal (BPLC) film. The number and wavelength of the lasing peaks can be manipulated by tuning the center of the bandgap, the order parameter of the laser dye, the quality of the resonance cavity, and even the pump energy. For single-wavelength lasing,  a lasing peak with an ultranarrow linewidth of 0.04 nm (Q-factor of 13 454) is achieved. Multiwavelength lasing is attained based on the following aspects: i) the narrow bandgaps of the BPLCs with full width at half maximum of 14-20 nm; ii) a laser dye with high gain over a wide wavelength band, having a low-order parameter in the liquid crystal matrix; iii) appropriate relative positions between the reflection and fluorescence peaks; and iv) the highly ordered crystal lattice of BPLC film. The proposed single-to-quadruple-wavelength surface-emitting lasers can be employed as coherent light sources for next-generation optical devices.

Diffusionless transformation of soft cubic superstructure from amorphous to simple cubic and body-centered cubic phases.

In a narrow temperature window in going from the isotropic to highly chiral orders, cholesteric liquid crystals exhibit so-called blue phases, consisting of different morphologies of long, space-filling double twisted cylinders. Those of cubic spatial symmetry have attracted considerable attention in recent years as templates for soft photonic materials. The latter often requires the creation of monodomains of predefined orientation and size, but their engineering is complicated by a lack of comprehensive understanding of how blue phases nucleate and transform into each other at a submicrometer length scale. In this work, we accomplish this by intercepting nucleation processes at intermediate stages with fast cross-linking of a stabilizing polymer matrix. We reveal using transmission electron microscopy, synchrotron small-angle X-ray diffraction, and angle-resolved microspectroscopy that the grid of double-twisted cylinders undergoes highly coordinated, diffusionless transformations. In light of our findings, the implementation of several applications is discussed, such as temperature-switchable QR codes, micro-area lasing, and fabrication of blue phase liquid crystals with large domain sizes.

Inkless Rewritable Photonic Crystals Paper Enabled by a Light-Driven Azobenzene Mesogen Switch.

Rewritable paper, as an environment-friendly approach of information transmission, has potential possibility to conserve energy and promote a sustainable development of our society. Recently, photonic crystals (PCs) have become a research hotspot in the development of rewritable paper. However, there are still many shortcomings that limit the further application of PC paper, such as slow response sensitivity, short-cycle lifetime, poor storage stability, and so on. Herein, we constructed an optically rewritable azobenzene inverse opals (AZOIOs) with a thin film (ca. 1 µm) plated on an inverse opal structure based on the UV/vis switchable structure color of the sample. The top thin film acts as a protective layer to avoid the large deformation of the pore structure and the bottom inverse opal structure with refractive index/pore structure change that provides reversible structure color. Large, reversible, and rapid bandgap shift (ca. 60 nm, 2 s) of AZOIOs can be repeated more than 100 times under alternating UV/vis irradiation based on isomerization of high content of the azobenzene group. On-demand long-time preservation pattern can be obtained by the appearance of azobenzene's intrinsic color. The proof of concept for rewritable PC paper is demonstrated herein. Such inkless rewritable colorful paper paves a way for developing novel display technology.

Photonic Shape Memory Polymer Based on Liquid Crystalline Blue Phase Films.

Photonic shape memory (SM) polymers based on liquid crystalline blue phase (BP) films have been fabricated by self-assembly and subsequent photopolymerization of liquid-crystal mixtures. These freestanding BP films exhibit narrow photonic band gaps and high reflectivity in the visible wavelength range. Multiple blue-shift colors are achieved by SM programming process at different mechanical pressures. The blue-shift colors can be attributed to a decrease of effective BP pitch along the viewing direction caused by the compressed deformation of the BP films, which are confirmed by a three-dimensional interometric profile. The deformed BP films can recover to their original shapes and reflecting colors by heating the polymer films to temperatures above the glass-transition temperature. Quantitative relationships between the shape change and optical response are established for understanding this SM effect. What is more, the temporary photonic patterns can be reversibly written and erased for dozens of cycles without apparent degradation, making these freestanding BP films appealing as rewritable photonic papers and optical sensors.

A UV-Responsive Multifunctional Photoelectric Device Based on Discotic Columnar Nanostructures and Molecular Motors.

Orientation control of ordered materials would not only produce new physical phenomenon but also facilitate the development of fancy devices. Discotic liquid crystals (DLCs) form 1D charge transport pathway by self-organizing into columnar nanostructures via π-π stacking. However, controlling the electrical properties in such nanostructures with some direct and instant way is a formidable task for their high viscosity and insensitivity to external stimuli. Herein, the arbitrary control over electrical conductivity of such columnar nanostructures is achieved with UV light by incorporating DLCs with molecular motors. Highly ordered DLC microstripe arrays are generated on desired substrate through a capillary bridge dewetting strategy. The conductivity of the microstripes could be continuously modulated by 365 nm light due to the influence of molecular motion under UV irradiation on the electron orbital overlap of columnar nanostructures. This is so because the disorder degree of the DLC molecules is associated with the intensity of UV light and the doping concentration of molecular motors. Moreover, the device shows memory effect and reversible conductivity change. The DLC microstripe arrays are very promising for the applications in UV detectors, memory devices, optical switches, and so on.

A Hydrophilic/Hydrophobic Janus Inverse-Opal Actuator via Gradient Infiltration.

Janus/gradient actuating materials have become promising candidates for actuating devices. The fabrication of functional Janus gradient actuators remains a challenge. This paper presents a facile fabrication of a hydrophilic/hydrophobic Janus inverse opal actuator via gradient infiltration. The Janus characteristics of the fabricated actuator were attributed to gradient infiltration along the thickness of the film caused by the gradient light intensity and the distinct polymerization behavior of ionic liquids and methyl methacrylate in the methanol system. The Janus film demonstrated directional bending upon water vapor adsorption, with a bending angle approaching 1440° in 4 s, accompanied by structure color/optic signal alteration. The actuating behaviors were effectively modulated by changing the composition of the film and the solvent system. Promising applications of this Janus solvent actuator were demonstrated in two sets of tests: driving an engine and lifting cargo. This work provides insight into the design and fabrication of multifunctional humidity-actuating materials.

Reversible solvent-sensitive actuator with continuous bending/debending process from liquid crystal elastomer-colloidal material.

A reversible solvent-sensitive actuator with a continuous bending/debending process is fabricated by over-infiltration of liquid crystal monomers into a colloidal template and subsequent photopolymerization. The fabricated actuator exhibits a maximum bending angle of 1080° in 1.58 s in dichloromethane, accompanied with successive debending in 0.32 s. The behavior of the actuator can be modulated by changing the solvent type, film thickness/length and molar ratio of A6OCB/C6M. This study will provide an important experimental and theoretical basis for the development of novel actuators.

Hydrogen-bonded metallo-supramolecular polymers based on ruthenium or iron complexes for the selective extraction of single-walled carbon nanotubes.

The chemical functionalization of nano-carbon materials such as single-walled carbon nanotubes (SWNTs) and graphene by metal complexes has attracted much attention due to the multitude of potential applications in efficient energy-conversion and -storage devices. The solubilization and single-chirality separation of SWNTs by surface modifications is a useful approach to manipulate SWNTs in the liquid phase. In this study, several Ru and Fe complexes containing two terminal quadruple hydrogen-bonded (H-bonded) ureidopyrimidinedione (UPy) groups were synthesized (Ru-1, Ru-UPy, and Fe-UPy) to form H-bonded supramolecular polymers by self-association. In order to control the solubility of these complexes in nonpolar solvents, Ru-UPy and Fe-UPy were endowed with long alkyl side chain groups in the coordinated 2,6-bis(benzimidazol-2-yl)pyridine ligand, while Ru-1 and Ru-2 do not contain such long alkyl chain groups. AFM measurements revealed that Ru-1, Ru-UPy, and Fe-UPy form a fiber-like network morphology on HOPG surfaces, arising from the H-bonded aggregation. However, only Ru-UPy and Fe-UPy are able to solubilize SWNTs effectively upon simple sonication in chlorobenzene. After the solubilization of a CoMoCAT® SWNT in chlorobenzene using Ru-UPy or Fe-UPy, UV-Vis-NIR spectra showed sharp peaks at 996 and 1150 nm, which were attributed to (6, 5) and (7, 6)-SWNTs. The Raman spectra of the solubilized SWNTs revealed peaks that were attributed to the radial breathing mode (RBM), which suggests an enrichment of semiconducting SWNTs, i.e., Ru-UPy and Fe-UPy are able to selectively solubilize semiconducting SWNTs. Cyclic voltammograms of films of SWNTs covered with Ru-UPy or Fe-UPy on ITO electrodes showed a well-defined adsorbed Ru(ii/iii) or Fe(ii/iii) wave. Upon addition of acid, the redox response from the adsorbed H-bonded Ru-UPy and Fe-UPy disappeared and only SWNTs were left on the ITO electrode. Moreover, the Ru-UPy/SWNT and Fe-UPy/SWNT hybrids exhibited non-linear I-V characteristics.

Patterning of Discotic Liquid Crystals with Tunable Molecular Orientation for Electronic Applications.

The large-area formation of functional micropatterns with liquid crystals is of great significance for diversified applications in interdisciplinary fields. Meanwhile, the control of molecular alignment in the patterns is fundamental and prerequisite for the adequate exploitation of their photoelectric properties. However, it would be extremely complicated and challenging for discotic liquid crystals (DLCs) to achieve the goal, because they are insensitive to external fields and surface chemistry. Herein, a simple method of patterning and aligning DLCs on flat substrates is disclosed through precise control of the formation and dewetting of the capillary liquid bridges, within which the DLC molecules are confined. Large-area uniform alignment occurs spontaneously due to directional shearing force when the solvent is slowly evaporated and programmable patterns could be directly generated on desired substrates. Moreover, the in-plane column direction of DLCs is tunable by slightly tailoring their chemical structures which changes their self-assembly behaviors in liquid bridges. The patterned DLCs show molecular orientation-dependent charge transport properties and are promising for templating self-assembly of other materials. The study provides a facile method for manipulation of the macroscopic patterns and microscopic molecular orientation which opens up new opportunities for electronic applications of DLCs.

Multi-functional organosilane-polymerized carbon dot inverse opals.

This paper demonstrates multi-functional optical properties of organosilane-polymerized carbon dot inverse opals, such as tricolor-fluorescence, fluorescence enhancement, multi-color micro-patterns for anti-fake applications and a thermally-induced blueshift of bandgaps. It is of significance for the design and fabrication of novel optical devices.

Photomobile Liquid-Crystalline Elastomers with Rearrangeable Networks.

Incorporation of dynamic covalent bonds into photomobile liquid-crystalline elastomers with a polysiloxane backbone enables the alignment of mesogens and macroscopic shapes to be controlled through the rearrangement of the network topology, even after the formation of chemically crosslinked networks. The reshaped samples show various sophisticated 3D motions upon irradiation with UV and visible light, depending on their initial shapes.

Photomobile polymer materials: photoresponsive behavior of cross-linked liquid-crystalline polymers with mesomorphic diarylethenes.

Cross-linked liquid-crystalline (LC) polymers with a mesomorphic diarylethene were prepared to demonstrate a versatile strategy for cross-linked photochromic LC polymers as photomobile materials. Upon exposure to UV light to cause photocyclization of the diarylethene chromophore, the cross-linked polymer films bend toward an actinic light source. By irradiation with visible light to cause a closed-ring to open-ring isomerization, the bent films revert to the initial flat state. Without visible-light irradiation, the bent films remain bent even at 120 °C, indicating high thermal stability of the cross-linked diarylethene LC polymers.

Depth-selective microscopic observation of a photomobile liquid crystal polymer under UV illumination.

By using the depth selective imaging method, we studied the UV induced change in a photomobile liquid crystalline polymer film. With 1 µm depth resolution, each slice inside the film was selectively observed. A network-like structure mixed with the ordered and disordered regions of molecules in the middle of the film, and a rubbed polymer layer at the bottom of the film were observed. In each slice of the film, the phase change induced by UV light was observed strongly dependent on the director direction, which indicates the ordering change of the liquid crystalline molecules in the director direction. It took several tens of seconds for the ordering change caused by the collaborative interaction between the molecules. Furthermore, it was suggested that the UV induced change travelled from the bottom layer to the middle layer on the micron order.

Photomobile polymer materials with crosslinked liquid-crystalline structures: molecular design, fabrication, and functions.

Crosslinked liquid-crystalline polymer materials that macroscopically deform when irradiated with light have been extensively studied in the past decade because of their potential in various applications, such as microactuators and microfluidic devices. The basic motions of these materials are contraction-expansion and bending-unbending, which are observed mainly in polysiloxanes and polyacrylates that contain photochromic moieties. Other sophisticated motions such as twisting, oscillation, rotation, and translational motion have also been achieved. In recent years, efforts have been made to improve the photoresponsive and mechanical properties of this novel class of materials through the modification of molecular structures, development of new fabrication methods, and construction of composite structures. Herein, we review structures, functions, and working mechanisms of photomobile materials and recent advances in this field.

Facile strain analysis of largely bending films by a surface-labelled grating method.

Mechanical properties of flexible films, for example surface strain of largely bending films, are key to design of stretchable electronic devices, wearable biointegrated devices, and soft microactuators/robots. However, existing methods are mainly based on strain-gauge measurements that require miniaturized array sensors, lead wires, and complicated calibrations. Here we introduce a facile method, based on surface-labelled gratings, for two-dimensional evaluation of surface strains in largely bending films. With this technique, we demonstrate that soft-matter mechanics can be distinct from the mechanics of hard materials. In particular, liquid-crystalline elastomers may undergo unconventional bending in three dimensions, in which both the inner and outer surfaces of the bending film are compressed. We also show that this method can be applied to amorphous elastomeric films, which highlights the general importance of this new mechanical evaluation tool in designing soft-matter-based electronic/photonic as well as biointegrated materials.

Photoinduced bending behavior of cross-linked azobenzene liquid-crystalline polymer films with a poly(oxyethylene) backbone.

Cross-linked azobenzene liquid-crystalline polymer films with a poly(oxyethylene) backbone are synthesized by photoinitiated cationic copolymerization. Azobenzene moieties in the film surface toward the light source are simultaneously photoaligned during photopolymerization with unpolarized 436 nm light and thus form a splayed alignment in the whole film. The prepared films show reversible photoinduced bending behavior with opposite bending directions when different surfaces of one film face to ultraviolet light irradiation.