The mechanical motion of materials has been increasingly explored in terms of bending and expansion/contraction. However, the locomotion of materials has been limited. Here, we report walking and rolling locomotion of chiral azobenzene crystals, induced thermally by a reversible single-crystal-to-single-crystal phase transition. Long plate-like crystals with thickness gradient in the longitudinal direction walk slowly, like an inchworm, by repeated bending and straightening under heating and cooling cycles near the transition temperature. Furthermore, thinner, longer plate-like crystals with width gradient roll much faster by tilted bending and then flipping under only one process of heating or cooling. The length of the crystal is shortened above the transition temperature, which induces bending due to the temperature gradient to the thickness direction. The bending motion is necessarily converted to the walking and rolling locomotion due to the unsymmetrical shape of the crystal. This finding of the crystal locomotion can lead to a field of crystal robotics.

Structural phase transitions induced by external stimuli such as temperature, pressure, electromagnetic fields, and light play crucial roles in controlling the functions of solid-state materials. Here we report a new phase transition, referred to as the photo-triggered phase transition, of a photochromic chiral salicylideneamine crystal. The crystal, which exhibits a thermal single-crystal-to-single-crystal phase transition which is reversible upon heating and cooling, transforms to the identical phase upon light irradiation at temperatures lower than the thermal transition temperature. The photo-triggered phase transition originates from the strain of trans-keto molecules produced by enol-keto photoisomerization owing to the small energy barrier associated with changes in the crystal structure. The photo-triggered phase is metastable and returns to the initial stable phase via back isomerization from the trans-keto to enol form.

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.

Photomechanically responsive materials are promising candidates for future smart actuator applications. The photo-responsive behaviors originate from the photoisomerization of photochromic molecules. A typical photochromic compound, azobenzene, has been studied extensively in the solution state and has played a crucial role in the photomechanical behaviors of materials such as polymers and gels, via chemical bridging with their matrix. In contrast to polymers and gels, the photomechanical attributes of molecular crystals have not progressed to the same degree, due to their rigidity and fragility. However, the past decade has witnessed an increasing number of reports of the photomechanical motion of molecular crystals, including azobenzene crystals. This paper reviews the current state-of-the-art of mechanically responsive azobenzene crystals, including the history, crystal design strategy, and future promising applications.

High frequency mechanical bending of the crystal was achieved based on the photothermal effect upon light irradiation.