The photoinduced crawling motion of crystals is a continuous motion that azobenzene molecular crystals exhibit under light irradiation. Such motion enables object manipulation at the microscale with a simple setup of fixed LED light sources. Transportation of nano-/micromaterials using photoinduced crawling motion has recently been reported. However, the details of the motion mechanism have not been revealed so far. Herein, we report visualization of the dynamics of fine particles in 4-(methylamino)azobenzene (4-MAAB) crystals under light irradiation via diffracted X-ray tracking (DXT). Continuously repeated melting and recrystallization of 4-MAAB crystals under light irradiation results in the flow of liquid 4-MAAB. Zinc oxide (ZnO) particles were introduced inside the 4-MAAB crystals to detect diffracted X-rays. The ZnO particles rotate with the flow of liquid 4-MAAB. By using white X-rays with a wide energy width, the rotation of each zinc oxide nanoparticle was detected as the movement of a bright spot in the X-ray diffraction pattern. It was clearly shown that the ZnO particles rotated increasingly as the irradiation light intensity increased. Furthermore, we also found anisotropy in the rotational direction of ZnO particles that occurred during the crawling motion of 4-MAAB crystals. It has become clear that the flow perpendicular to the supporting film of 4-MAAB crystals is enhanced inside the crystal during the crawling motion. DXT provides a unique means to elucidate the mechanism of photoinduced crawling motion of crystals.
Materials that exhibit actuation behaviour in response to external stimuli have a wide range of applications owing to their ability to convert input energy into mechanical work. Light and chemicals are common sources of input energy. However, actuation using thermal energy from ambient-temperature sources remains challenging. In this study, we introduce novel elastic crystals composed of dodecylated porphyrin molecules that exhibit high flexibility and deformation in response to temperature changes. When a crystal is loaded with a small weight and positioned between high- and low-temperature heat sources, it exhibited continuous, large, and rapid oscillations. These oscillations persisted for at least 160 h, corresponding to 3.9 million deformation cycles, as long as the temperature difference was maintained. This study presents the first example of a molecular crystal functioning as an engine that can extract kinetic energy from static and ambient-temperature sources.