Mechanical Motion of Chiral Azobenzene Crystals with Twisting upon Photoirradiation

The photomechanical motion of chiral crystals of trans‐azobenzene derivatives with an (S)‐ and (R)‐phenylethylamide group was investigated and compared with a racemic crystal. Changes in the UV/Vis absorption spectra of the powdered crystals before and after UV irradiation were measured by using an optical waveguide spectrometer, showing that the lifetime of the cis‐to‐trans thermal back‐isomerization of the chiral crystals was faster than that of the racemic crystals. Upon UV irradiation, a long plate‐like chiral microcrystal bent away from the light source with a twisting motion. A square‐like chiral microcrystal curled toward the light with some twisting. Reversible bending of a rod‐like chiral microcrystal was repeatable over twenty‐five cycles. In contrast, bending of a plate‐like racemic microcrystal was small. A possible mechanism for the bending and twisting motion was discussed based on the optimized cis conformer determined by using calculations, showing that the bending motion with twisting is caused by elongation along the b axis and shrinkage along the a axis.     

Light‐Induced Bending of Needle‐Like Crystals of Naphthylvinylbenzoxazole Triggered by trans–cis Isomerization

New diarylethene derivatives containing benzoxazole ( NBO ) and benzothiazole ( NBT ) have been synthesized. Light‐induced trans–cis isomerization of NBO and NBT took place in crystals, and only induced the needle‐like crystals of NBO to bend backwards away from the UV light source. The movement of the atoms was deemed to take place during the isomerization of NBO ; hence, strain would be produced and accumulated rapidly in the surface of crystals exposed to UV light. The uniform release of strain led to the bending of needle‐like crystals. The light‐induced trans–cis isomerization efficiency of NBT was too low to drive the motion of crystals, which might have originated from the large repulsion between naphthyl and benzothiazole. These results provide a new platform for the transformation of light energy into mechanical energy in molecular crystals through the unimolecular photochemical reaction of diarylethene derivatives.     

Guided Self‐Propelled Leaping of Droplets on a Micro‐Anisotropic Superhydrophobic Surface

By introducing anisotropic micropatterns on a superhydrophobic surface, we demonstrate that water microdroplets can coalesce and leap over the surface spontaneously along a prescribed direction. This controlled behavior is attributed to anisotropic liquid–solid adhesion. An analysis relating the preferential leaping probability to the geometrical parameters of the system is presented with consistent experimental results. Surfaces with this rare quality demonstrate many unique characteristics, such as self‐powered, and relatively long‐distance transport of microdroplets by “relay” coalescence‐induced leaping.     

A Light‐Activated Polymer Composite Enables On‐Demand Photocontrolled Motion: Transportation at the Liquid/Air Interface

Swimmers at liquid/air interfaces have drawn enormous attention because of their potential applications. Described herein is one novel light‐driven swimmer based on a bimorph composite structure of a photoresponsive liquid‐crystalline polymer network and a commercially available polyimide (Kapton). The motion of the swimmer can be controlled by photoirradiation. The bilayer‐structured film shows quickly photoinduced bending towards the Kapton side upon exposure to UV light, and recovers immediately after removal of light. When placed on a liquid surface, the swimmer propels itself continually though rhythmic beating the liquid like a dolphin moving forward with its tail fin. Besides, light‐powered rotation of the swimmer is successfully achieved by simply changing the length‐width ratio and the irradiation site, mimicking the function of a dolphin's pectoral fin. Combining the forward movement and rotation motion together, on‐demand directional control of the photo‐driven swimmer can be readily obtained at room temperature, showing promise for miniaturized units for transportation.     

Photoinduced swing of a diarylethene thin broad sword shaped crystal: a study on the detailed mechanism

We report a swinging motion of photochromic thin broad sword shaped crystals upon continuous irradiation with UV light. By contrast in thick crystals, photosalient phenomena were observed. The bending and swinging mechanisms are in fact due to molecular size changes as well as phase transitions. The first slight bending away from the light source is due to photocyclization-induced surface expansion, and the second dramatic bending toward UV incidence is due to single-crystal-to-single-crystal (SCSC) phase transition from the original phase I to phase II_UV. Upon visible light irradiation, the crystal returned to phase I. A similar SCSC phase transition with a similar volume decrease occurred by lowering the temperature (phase III_temp). For both photoinduced and thermal SCSC phase transitions, the symmetry of the unit cell is lowered; in phase II_UV the twisting angle of disordered phenyl groups is different between two adjacent molecules, while in phase III_temp, the population of the phenyl rotamer is different between adjacent molecules. In the case of phase II_UV, we found thickness dependent photosalient phenomena. The thin broad sword shaped crystals with a 3 μm thickness showed no photosalient phenomena, whereas photoinduced SCSC phase transition occurred. In contrast, large crystals of several tens of μm thickness showed photosalient phenomena on the irradiated surface where SCSC phase transition occurred. The results indicated that the accumulated strain, between isomerized and non-isomerized layers, gave rise to the photosalient phenomenon.

We report a swinging motion of photochromic thin broad sword shaped crystals upon continuous irradiation with UV light.     

Mechanical Effects of Elastic Crystals Driven by Natural Sunlight and Force

Flexible crystals that can capture solar energy and convert it into mechanical energy are promising for a wide range of applications such as information storage and actuators, but obtaining them remains a challenge. Herein, an elastic crystal of a barbiturate derivative was found to be an excellent candidate, demonstrating plastic bending behavior under natural sunlight irradiation. ¹H NMR and high-resolution mass spectrum data of microcrystals before and after light irradiation demonstrated that light-induced [2+2] cycloaddition was the driving force for the photomechanical effects. Interestingly, the crystals retained elastic bending even after light irradiation. This is the first report of flexible crystals that can be driven by natural sunlight and that have both photomechanical properties and elasticity. Furthermore, regulation of the passive light output direction of the crystals and transport of objects by applying mechanical forces and light was demonstrated.     

A Multifunctional Dye‐doped Liquid Crystal Polymer Actuator: Light‐Guided Transportation,Turning in Locomotion,and Autonomous Motion

A strip of a liquid crystal elastomer doped with a near‐infrared dye with one side crosslinked monodomain and the other crosslinked polydomain along the thickness behaves like a multifunctional photoactuator without the need for a support. A flat strip with two ends fixed on substrate surface forms a moving bump under laser scanning, which can be used as light‐fueled conveyor to transport an object. Cutting off and laser scanning the bump with two free ends makes a soft and flexible millimeter‐scale crawler that can not only move straight and climb an inclined surface, but also undergo light‐guided turning to right or left as a result of combined out‐of‐plane and in‐plane actuation. Based on the self‐shadowing mechanism, with one end of the strip fixed on substrate surface, it can execute a variety of autonomous arm‐like movements under constant laser illumination, such as bending–unbending and twisting, depending on the laser incident angles with respect to the strip actuator.     

A Multifunctional Dye‐doped Liquid Crystal Polymer Actuator: Light‐Guided Transportation,Turning in Locomotion,and Autonomous Motion

A strip of a liquid crystal elastomer doped with a near‐infrared dye with one side crosslinked monodomain and the other crosslinked polydomain along the thickness behaves like a multifunctional photoactuator without the need for a support. A flat strip with two ends fixed on substrate surface forms a moving bump under laser scanning, which can be used as light‐fueled conveyor to transport an object. Cutting off and laser scanning the bump with two free ends makes a soft and flexible millimeter‐scale crawler that can not only move straight and climb an inclined surface, but also undergo light‐guided turning to right or left as a result of combined out‐of‐plane and in‐plane actuation. Based on the self‐shadowing mechanism, with one end of the strip fixed on substrate surface, it can execute a variety of autonomous arm‐like movements under constant laser illumination, such as bending–unbending and twisting, depending on the laser incident angles with respect to the strip actuator.     

Photoinduced Ratchet‐Like Rotational Motion of Branched Molecular Crystals

Photomechanical molecular crystals can undergo a variety of light‐induced motions, including expansion, bending, twisting, and jumping. The use of more complex crystal shapes may provide ways to turn these motions into useful work. To generate such shapes, pH‐driven reprecipitation has been used to grow branched microcrystals of the anthracene derivative 4‐fluoroanthracenecarboxylic acid. When these microcrystals are illuminated with light of λ=405 nm, an intermolecular [4+4] photodimerization reaction drives twisting and bending of the individual branches. These deformations drive a rotation of the overall crystal that can be repeated over multiple exposures to light. The magnitude and direction of this rotation vary because of differences in the crystal shape, but a typical branched crystal undergoes a 50° net rotation after 25 consecutive irradiations for 1 s. The ability of these crystals to undergo ratchet‐like rotation is attributed to their chiral shape.     

Fabrication of Light‐Triggered Soft Artificial Muscles via a Mixed‐Matrix Membrane Strategy

Artificial muscles triggered by light are of great importance, especially for the development of non‐contact and remotely controlled materials. Common materials for synthesis of photoinduced artificial muscles typically rely on polymer‐based photomechanical materials. Herein, we are able to prepare artificial muscles using a mixed‐matrix membrane strategy to incorporate photomechanical molecular crystals with connective polymers (e.g. PVDF). The formed hybrid materials inherit not only the advantages of the photomechanical crystals, including faster light response, higher Young's modulus and ordered structure, but also the elastomer properties from polymers. This new type of artificial muscles demonstrates various muscle movements, including lifting objects, grasping objects, crawling and swimming, triggered by light irradiation. These results open a new direction to prepare light‐driven artificial muscles based on molecular crystals.     

Bidirectional Photomodulation of Surface Tension in Langmuir Films

Switching systems operating in a cooperative manner capable of converting light energy into mechanical motion are of great interest for optical devices, data storage, nanoscale energy converters and molecular sensing. Herein, photoswitchable monolayers were formed at the air–water interface from either a pure bis(thiaxanthylidene)‐based photoswitchable amphiphile or from a mixture of the photoswitchable amphiphile with a conventional lipid dipalmitoylphosphatidylcholine (DPPC). Efficient photoisomerization of the anti ‐folded to syn ‐folded geometry of the amphiphile's central core induces changes in the surface pressure in either direction, depending on the initial molecular density. Additionally, the switching behavior can be regulated in the presence of DPPC, which influences the packing of the molecules, thereby controlling the transformation upon irradiation. Bis(thiaxanthylidene)‐based photoswitchable monolayers provide a promising system to explore cooperativity and amplification of motion.     

Synthesis and Characterization of a Soluble Polyimide Containing a Photoreactive 4‐Styrylpyridine Derivative as the Side Group

An aromatic polyimide bearing photoreactive 4‐(2‐(4‐oxyethylenyloxyphenyl)vinyl)pyridine side groups was synthesized and characterized. The polymer is stable up to 300°C and soluble in organic solvents, giving thin films in good quality. When exposed to UV light, it reorients favorably with an angle of 98° with respect to the electric vector of linearly polarized UV light. UV‐exposed films align liquid‐crystals (LCs) homogeneously along the preferential orientation of the polymer chains on the surface. The pretilt angle of the LCs is 0.32–0.92°, depending on the exposure dose and annealing. LC alignment is retained up to 210°C. Based on the optical retardation behavior and spectroscopic measurements, a photoalignment mechanism is proposed.     

Thermo-Induced Single-Crystal-to-Single-Crystal Transformations and Photo-Induced [2+2] Cycloaddition Reactions in Polymorphs of Chalcone-Based Molecular Crystals: Multi-Stimuli Responsive Actuators

The polymorphs of 2ClChMe-4 in Form I (ribbon-like crystal) and Form II (block-like crystal) were prepared, and they exhibited curling/flipping and expansion upon heating on account of single-crystal-to-single-crystal transformations. The irreversible phase transformations occurred separately at 53.2 °C and 57.8 °C for the crystals in Form I and Form II, during which the molecular conformation of 2ClChMe-4 changed and the molecules slipped along the (100) plane. Movement at the molecular level resulted in changes of cell parameters, which in turn led to macroscopic motions of the crystals upon heating. Additionally, the ribbon-like crystals of 2ClChMe-4 showed photo-induced bending driven by [2+2] cycloaddition. Accordingly, an actuator showing reversible bending behavior was fabricated triggered by light and heat successively. Like biomimetic self-actuators, such multi-stimuli mechanical responsive molecular crystals might have potential applications in soft robots, artificial muscles and microfluidic systems.     

Photoinduced Reversible Topographical Changes on Diarylethene Microcrystalline Surfaces with Biomimetic Wetting Properties

Reversible topographical changes were observed on a photochromic diarylethene microcrystalline film surface by alternate irradiation with UV and visible light. Two types of surfaces were prepared from this film: 1) Storage of the film at 30 °C for 24 hours in the dark after UV irradiation afforded a surface that was covered with needle‐shaped crystals, whose diameter and length were approximately 1 μm and 10 μm, respectively, and showed a superhydrophobic lotus effect. 2) Storage of the film at 70 °C for 3 hours in the dark caused the needle‐shaped crystals to be converted into larger rod‐like crystals (5∼8 μm wide and 20∼30 μm long) by Ostwald ripening and a disappearance of the lotus effect. The obtained activation energy of the formation of the needle‐ and rod‐shaped crystals was 143 and 162 kJ mol⁻¹, respectively. Subsequent UV irradiation to the surface, which was followed by storage at 50 °C for 1 hour in the dark, gave a doubly rough structure; small needle‐shaped crystals were formed between the larger rod‐shaped crystals. The surface showed both superhydrophobic properties and the pinned effect of the water droplet: the petal effect. Fractal analysis of both surfaces were carried out using a box‐counting method, and the lotus effect was observed in the presence of smaller‐sized crystals, whilst the petal effect was observed with larger sized crystals (ca. 100 μm). We demonstrated that the hydrophobic property was controlled by the distribution in crystal size of the closed‐ring isomer of the diarylethene. Visible‐light irradiation of both rough surfaces afforded surfaces with cubic‐shaped micro‐crystals of the open‐ring isomer.     

Thermoresponsive Polymer Brush Modulation on the Direction of Motion of Phoretically Driven Janus Micromotors

We report a thermoresponsive poly(N‐isopropylacrylamide) (PNIPAM) brush functionalized Janus Au–Pt bimetallic micromotor capable of modulating the direction of motion with the change of the ambient temperature. The PNIPAM@Au–Pt micromotor moved along the Au–Pt direction with a speed of 8.5 μm s^?1 in 1.5 % H₂O₂ at 25 °C (below the lower critical solution temperature (LCST) of PNIPAM), whereas it changed the direction of motion (i.e., along the Pt–Au direction) and the speed decreased to 2.3 μm s^?1 at 35 °C (above LCST). Below LCST, PNIPAM brushes grafted on the Au side were hydrophilic and swelled, which permitted the electron transfer and proton diffusion on the Au side, and thus the motion is regarded as a self‐electrophoretic mechanism. However, PNIPAM brushes above LCST became hydrophobic and collapsed, and thus the driving mechanism switched to the self‐diffusiophoresis like that of Pt‐modified Janus silica motors. These motors could reversibly change the direction of motion with the transition of the hydrophobic and hydrophilic states of the grafted PNIPAM brushes. Such a thermoresponsive polymer brush functionalization method provides a new strategy for engineering the kinematic behavior of phoretically driven micro/nanomotors.     

Morphosynthesis of poly[4‐(1,4‐phenylene)oxyphthalimide] and copolymers prepared by reaction‐induced crystallization during polymerization

Morphosynthesis of poly[4‐(1,4‐phenylene)oxyphthalimide] (POPI) and poly[4‐(1,4‐phenylene)oxyphthalimide‐co‐4‐phthalimide] (POPI‐PPI) was examined by using the crystallization during the polymerization. The POPI fibrillar crystals were obtained as precipitates with the formation of spherical aggregates of plate‐like crystals. Some of the POPI fibrillar crystals were longer than 15 μm. They possessed high crystallinity and the molecules aligned perpendicular to the long direction of the fibers. On the other hand, one‐dimensional structures of POPI‐PPI such as ribbon, cone, rod, and fiber were obtained as precipitates by the copolymerization. The copolymer molecules might align along the long direction of the cone‐like crystals. The morphology of these poly(ether‐imide)s could be controlled by not only the polymerization condition but also with the aid of copolymerization. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Piezoreflectance spectra of 1s Z12 exciton in CuBr

We have investigated the piezoreflectance spectra (deltaR/R) of the 1s Z12 exciton in single crystals of copper bromide CuBr at the temperature of 95 K with linearly polarized light. The spectra were successively studied with the pressure p along the [001] and [111] axis and the wave vector k of the incident light parallel to the [110] direction. The shear deformation potentials b and d of the 1s Z12 exciton were deduced from the stress-induced shift and splitting. The results are compared with those obtained in other works.     

Photocontrolled manipulation of a microscale object: a rotational or translational mechanism

In this paper the photocontrolled manipulation of solid materials on the surface of a liquid crystalline thin film is described. Three different types of films namely cholesteric liquid crystal (ChLC), compensated nematic liquid crystal (NLC) and nematic LC were used. The rotational and translational manipulation of the microscale solid object was induced by irradiation of light and mode of manipulation (either translational or rotational) was changed by changing the isomer of the azobenzene compound used to make the film. Rotational motion of the object was observed on the ChLC and compensated NLC films containing chirally pure azobenzene compound. The direction of rotational motion was controlled either by changing the optical isomer of the chiral azobenzene or by changing the irradiating light (from ultraviolet to visible). When racemic mixture of the chiral azobenzene compound was used, a translational motion of the object was observed. Even though the direction of the translational motion can be controlled by controlling irradiation position, more facile and precise manipulation of the objects was possible by spatially controlled irradiation of Ar(+) laser and diode UV laser.     

Microwave-assisted self-organization of colloidal particles in confining aqueous droplets

Monodisperse aqueous emulsion droplets encapsulating colloidal particles were produced in the oil phase, and controlled microwave irradiation of the aqueous drop phase created spherical colloidal crystals by so-called evaporation-induced self-organization of the colloidal particles. Unlike usual colloidal crystals, colloidal crystals in spherical symmetry (or photonic balls) possessed photonic band gaps for the normal incident light independent of the position all over the spherical surface. While the consolidation of colloidal particles in emulsion droplets in an oven took several hours, the present microwave-assisted evaporation could reduce the time for complete evaporation to a few tens of minutes. Under the microwave irradiation, the aqueous phase in emulsions was superheated selectively and the evaporation rate of water could be controlled easily by adjusting the microwave intensity. The result showed that the packing quality of colloidal crystals obtained by the microwave-assisted self-organization was good enough to show photonic band gap characteristics. The reflectance of our photonic balls responded precisely to any change in physical properties including the size of colloidal particles, refractive index mismatch, and angle of the incident beam. In particular, for polymeric particles, the photonic band gap could be tuned by the intensity of microwave irradiation, and the reflection color was red-shifted with stronger microwave irradiation. Finally, for better photonic band gap properties, inverted photonic balls were prepared by using the spherical colloidal crystals as sacrificial templates.     

Thickness-dependent molecular chain and lamellar crystal orientation in ultrathin poly(di-n-hexylsilane) films

The molecular chain and lamellar crystal orientation in ultrathin films (thickness < 100 nm) of poly-(di-n-hexylsilane) (PDHS) on silicon wafer substrates have been investigated by using transmission electronic microscopy, wide-angle X-ray diffraction, atomic force microscopy, and UV absorption spectroscopy. PDHS showed a film thickness-dependent molecular chain and lamellar crystal orientation. Lamellar crystals grew preferentially in flat-on orientation in the monolayer ultrathin films of PDHS, i.e., the silicon backbones were oriented along the surface-normal direction. By contrast, the orientation of lamellar crystals was preferentially edge-on in ultrathin films thicker than ca. 13 nm, i.e., the silicon backbones were oriented parallel to the substrate surface. We interpret the different orientations of molecular chain and lamellar crystal as due to the reduction of the entropy of the polymer chain near the substrate surface and the particularity of the crystallographic (001) plane of flat-on lamellae, respectively. A remarkable influence of the orientations of the silicon backbone on the UV absorption of these PDHS ultrathin films was observed due to the one-dimensional nature of sigma-electrons delocalized along the silicon backbone. With the silicon backbones perpendicular or parallel to the surface of the substrate, the UV absorbance increased or decreased with an increase of the angle between the incident UV beam direction and direction normal to the thin film, respectively.