Mechanically responsive crystals have been increasingly explored, mainly based on photoisomerization. However, photoisomerization has some disadvantages for crystal actuation, such as a slow actuation speed, no actuation of thick crystals, and a narrow wavelength range. Here we report photothermally driven fast-bending actuation and simulation of a salicylideneaniline derivative crystal with an o-amino substituent in enol form. Under ultraviolet (UV) light irradiation, these thin (<20 μm) crystals bent but the thick (>40 μm) crystals did not due to photoisomerization; in contrast, thick crystals bent very quickly (in several milliseconds) due to the photothermal effect, even by visible light. Finally, 500 Hz high-frequency bending was achieved by pulsed UV laser irradiation. The generated photothermal energy was estimated based on the photodynamics using femtosecond transient absorption. Photothermal bending is caused by a nonsteady temperature gradient in the thickness direction due to the heat conduction of photothermal energy generated near the crystal surface. The temperature gradient was calculated based on the one-dimensional nonsteady heat conduction equation to simulate photothermally driven crystal bending successfully. Most crystals that absorb light have their own photothermal effects. It is expected that the creation and design of actuation of almost all crystals will be possible via the photothermal effect, which cannot be realized by photoisomerization, and the potential and versatility of crystals as actuation materials will expand in the near future.

Molecular crystals have shown remarkable adaptability in response to a range of external stimuli. Here, we survey this emerging field and provide a critical overview of the experimental, computational and instrumental tools being used to design and apply such materials.

Mechanically responsive materials have been investigated extensively over the past two decades. Diversification of actuation modes is essential for the practical application of mechanical materials. Polymorphic crystals with different crystal structures composed of the same compound can exhibit distinct mechanical motions. Here, we focused on two polymorphs of a salicylideneaniline derivative with a 4-fluoro substituent in enol form, 1α and 1β, and investigated their different photomechanical behaviors. Under ultraviolet (UV) light irradiation, the thin plate-like 1α crystal bent away gradually and strongly from the light source, with some twist caused by enol–keto photoisomerization. In contrast, the thin, needle-like 1β crystal did not bend by photoisomerization; however, the thick 1β crystal bent away quickly from the light source because of the photothermal effect, ultimately achieving 500 Hz high-speed bending under pulsed UV laser irradiation. Moreover, the thick plate-like 1α crystal exhibited two-step motion: fast bending forward by the photothermal effect and then slow bending away by photoisomerization. We succeeded in creating four motions using two polymorphic crystals and two distinct mechanisms, thereby providing a novel approach to diversify the mechanical motions of molecular crystals and expanding the potential and versatility of molecular crystals as actuation materials.

Photomechanical molecular crystals have been developed over the past two decades, and actuation switching is an important requirement for their practical application. In this study, we developed a method for...

Mechanically responsive molecular crystals that exhibit macroscopic motions such as bending, twisting, and locomotion by light and heat have been studied intensively over the past decade. Photoisomerization has been applied to induce various motions, especially the bending of typical photochromic crystals, e. g., diarylethene and azobenzene. Phase transition is another mechanism underlying crystal actuation. Moreover, photothermal effect is a promising mechanism that has the potential to actuate any crystals that absorb light, including those for which actuation cannot be achieved by photoisomerization or phase transitions. Molecular crystals have an advantage over polymers and gels in terms of having a higher elastic modulus and stronger output force. However, previous studies of mechanical crystals have been limited mostly to basic research. There is a need to address the practical application of such mechanically responsive crystals in sensors, switches, actuators, and soft robots.