Atsushi Shishido

Photomobile polymer materials—various three-dimensional movements

The composition of a crosslinked azobenzene liquid-crystalline polymer and a flexible polymer film can provide a variety of simple devices that can walk in one direction like an ‘inchworm’ and move like a ‘robotic arm’ induced by light.

Azobenzene photomechanics: prospects and potential applications

The change in shape inducible in some photo-reversible molecules using light can effect powerful changes to a variety of properties of a host material. This class of reversible light-switchable molecules includes molecules that photo-dimerize, such as coumarins and anthracenes; those that allow intra-molecular photo-induced bond formation, such as fulgides, spiro-pyrans, and diarylethenes; and those that exhibit photo-isomerization, such as stilbenes, crowded alkenes, and azobenzenes. The most ubiquitous natural molecule for reversible shape change, however, and perhaps the inspiration for all artificial bio-mimics, is the rhodopsin/retinal protein system that enables vision, and this is the quintessential reversible photo-switch for performance and robustness. Here, the small retinal molecule embedded in a cage of rhodopsin helices isomerizes from a cis geometry to a trans geometry around a C=C double bond with the absorption of just a single photon. The modest shape change of just a few angstroms is quickly amplified and sets off a cascade of larger shape and chemical changes, eventually culminating in an electrical signal to the brain of a vision event, the energy of the input photon amplified many thousands of times in the process. Complicated biochemical pathways then revert the trans isomer back to cis, and set the system back up for another cascade upon subsequent absorption. The reversibility is complete, and many subsequent cycles are possible. The reversion mechanism back to the initial cis state is complex and enzymatic, hence direct application of the retinal/rhodopsin photo-switch to engineering systems is difficult. Perhaps the best artificial mimic of this strong photo-switching effect however in terms of reversibility, speed, and simplicity of incorporation, is azobenzene. Trans and cis states can be switched in microseconds with low-power light, reversibility of 105 and 106 cycles is routine before chemical fatigue, and a wide variety of molecular architectures is available to the synthetic materials chemist, permitting facile anchoring and compatibility, as well as chemical and physical amplification of the simple geometric change. This review article focuses on photo-mechanical effect taking place in various material systems incorporating azobenzene. The photo-mechanical effect can be defined as reversible change in shape by absorption of light, which results in a significant macroscopic mechanical deformation, and reversible mechanical actuation, of the host material. Thus, we exclude simple thermal expansion effects, reversible but non-mechanical photo-switching or photo-chemistry, as well as the wide range of optical and electro-optical switching effects for which good reviews exist elsewhere. Azobenzene-based material systems are also of great interest for light energy harvesting applications across much of the solar spectrum, yet this emerging field is still in an early enough stage of research output as to not yet warrant review, but we hope that some of the ideas put forward here toward promising future directions of research, will help guide the field.

Fabrication of two-dimensional photonic crystals using interference lithography and electrodeposition of CdSe

This letter describes a simple synthetic approach to fabricate two-dimensional midinfrared CdSe photonic crystals (PC) by electrodeposition of CdSe in a polymer template defined using interference lithography. Characterization of the transmission spectra of CdSe PCs with a hexagonal array of 1.3 μm diameter and 2.7 μm pitch air voids showed a well-defined drop in transmission at 4.23 μm. The drop in transmission increased with incident angle, reaching a maximum of approximately 2.6 dB at 40° relative to the surface normal. This two-step synthetic approach can be used to incorporate photonic crystals onto arbitrary substrates for integration into future advanced optical circuits.

Effect of concentration of photoactive chromophores on photomechanical properties of crosslinked azobenzene liquid-crystalline polymers

We studied the effects of concentration and location of azobenzene chromophores on the photoinduced deformation of crosslinked liquid-crystalline polymers (CLCPs). The concentration of azobenzene chromophores in CLCP affects the degree of isomerization of azobenzene moieties and the macroscopic deformation behaviour of the films while the location of azobenzene moieties determines the contraction force and length.

Recent twists in photoactuation and photoalignment control

The design of functional and stimuli-responsive materials is among the key goals of modern materials science. The structure and properties of such materials can be controlled via various stimuli, among which light is often times the most attractive choice. Light is ubiquitous and a gentle energy source and its properties can be optimized for a specific target remotely, with high spatial and temporal resolution. Light-control over molecular alignment has in recent years attracted particular interest, for potential applications such as reconfigurable photonic elements and optical-to-mechanical energy conversion. Herein, we bring forward some recent examples and emerging trends in this exciting field of research, focusing on liquid crystals, liquid-crystalline polymers and photochromic organic crystals, which we believe serve to highlight the immense potential of light-responsive materials to a wide variety of current and future high-tech applications in photonics, energy harvesting and conversion.

Direct fabrication of two-dimensional titania arrays using interference photolithography

Two-dimensional (2D) titania arrays with periods of 0.8–2.0 μm were fabricated by polymerization of a photosensitive titanium-containing monomer film using interference photolithography. The 2D precursor arrays were prepared by exposing a mixture of methacrylic acid, ethyleneglycol dimethacrylate, and titanium ethoxide doped with photoinitiator to 355 nm, 15 ns pulses from a Nd-Yttrium–aluminum–garnet laser and then rinsing with methanol. Pure titania arrays were obtained from the precursor arrays by subsequent calcination at 575 °C. The structure of the arrays fabricated by this method was confirmed with optical microscopy and scanning electron microscopy.

Dipalladium Catalyst for Olefin Polymerization: Introduction of Acrylate Units into the Main Chain of Branched Polyethylene†

A dipalladium complex with a double-decker structure catalyzes ethylene-acrylate copolymerization to produce the branched polymer containing the acrylate units in the polymer chain, not at the branch terminus. The cooperation of the two palladium centers, which are fixed in a rigid framework of the macrocyclic ligand, is proposed to have a significant dinuclear effect on the copolymerization.

All-optical image processing by means of a photosensitive nonlinear liquid-crystal film: edge enhancement and image addition-subtraction.

We demonstrate two simple yet efficient all-optical image-processing techniques that use nonlinear photosensitive dye-doped nematic liquid-crystal films, namely, edge enhancement and image addition-subtraction operations. These films require no external bias and function at much lower optical powers and shorter response times than other conventional methods.

Simultaneous Analysis of Optical and Mechanical Properties of Cross-Linked Azobenzene-Containing Liquid-Crystalline Polymer Films

The photomechanical behavior of cross-linked azobenzene-containing liquid-crystalline polymer films was investigated by means of simultaneous measurement of their optical and mechanical properties. The connection between photoisomerization of the azobenzene moieties, photoinduced change in molecular alignment, photoinduced stress generation, and macroscopic bending was analyzed. Upon UV irradiation, the films exhibited bending due to gradient in cis-azobenzene content, and subsequent unbending when cis-azobenzene content became uniform throughout the film. The maximum photoinduced stress was generated in the same time scale as the time required to reach photostationary state in the cis-azobenzene concentration. The maximum values of photogenerated stress strongly depended on the crosslinker concentration, even if the azobenzene concentration and the cis-azobenzene content in the photostationary state were similar for all the polymer films. The stress is connected to the initial Youngs modulus and also to the photoinduced change in birefringence of the polymer films. In addition, a significant photoinduced decrease in Youngs modulus was for the first time observed in cross-linked azobenzene-containing liquid-crystalline polymers, which is likely to be an important factor in dictating their photomechanical behavior.

High-Contrast Photoswitching of Nonlinear Optical Response in Crosslinked Ferroelectric Liquid-Crystalline Polymers

A conceptually novel materials design, based on crosslinked ferroelectric liquid-crystalline polymers, is demonstrated for efficient switching of a second-order nonlinear optical (NLO) response in the solid state. By controlling the molecular alignment of the NLO moieties through two-photon isomerization of azobenzene molecules, reversible isothermal photocontrol of second-harmonic generation is achieved with contrast of up to 20.