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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., (© 2021 Wiley-VCH GmbH.)

Three groups of chalcone derivatives and their analogues involving halogen atoms (X=F, Cl, Br) have been synthesized. Firstly, the nearly planar acyclic chalcone derivatives were inclined to undergo photo‐induced stereospecific [2+2] cycloaddition, which triggered the crystals to exhibit macroscopic motions of bending or cracking. In particular, the single‐crystal‐to‐single‐crystal transformation happened upon UV irradiation of the crystals, which was helpful for the understanding photomechanical effects. Cyclic 3,4‐dihydronaphthalene‐based chalcone analogues possess a more twisted conformation, and they tend to undergo trans‐cis isomerization. No photomechanical effect was observed for the crystals of the cyclic chalcone analogues due to the lower isomerization rate. The twist degree of chroman‐based molecules was in between of the first two, [2+2] cycloaddition and trans‐cis isomerization simultaneously took place in crystals. Photo‐induced bending and twisting were observed for the crystals of chroman‐based chalcone analogues. Therefore, the differences in molecular dihedral angles in α,β‐unsaturated ketones were responsible for their photochemical characters and in turn to tune the photomechanical effects. In this work, a bridge between the molecular structures and solid‐state photochemical reactions triggered photomechanical crystals is built. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Fluorine-free chalcones and chalcones bearing different numbers of fluorine atoms have been synthesized. It is found that fluorine can tune the reactivity of photo-induced [2 + 2] cycloaddition reactions in crystals. The higher the number of fluorine atoms, the higher the reactivity of the photodimerization. The single crystal structures and Hirshfeld surface analysis illustrated that the introduction of fluorine not only increased the molecular planarity but could also steer the potentially reactive double bonds in appropriate positions of the crystal lattices to meet Schmidt's criteria. Therefore, the stereospecific [2 + 2] cycloaddition reactions took place to afford one diastereoisomer from the reactive chalcones except for (E)-3-(4-fluorophenyl)-1-phenylprop-2-en-1-one (1FChH). Additionally, the chalcone-based molecular crystals exhibited various photomechanical behaviors, such as bending toward or away from the light source, swinging, cracking and jumping, driven by topo-photoreactions. As expected, the more efficient photo-induced [2 + 2] cycloaddition reactions in crystalline states led to more significant motions of the molecular crystals. Powder X-ray diffraction results suggested that the solid state [2 + 2] cycloaddition reactions changed the unit cell of the single crystals. The photo-induced bending toward or away from the light source for the needle-like crystals originated from the contraction or the expansion of the phototropic surface. Hence, the robust balancer fluorine in chalcones might play an important role in the crystalline packing. This provides a facile approach in crystal engineering to fabricate photo-induced mechanically responsive crystalline materials. [ABSTRACT FROM AUTHOR]