Engineering Photomechanical Molecular Crystals to Achieve Extraordinary Expansion Based on Solid-State [2 + 2] Photocycloaddition.

Abstract

Photomechanical molecular crystals are promising candidates for photoactuators and can potentially be implemented as smart materials in various fields. Here, we synthesized a new molecular crystal, (E)-3-(naphthalen-1-yl)acrylaldehyde malononitrile ((E)-NAAM), that can undergo a solid-state [2 + 2] photocycloaddition reaction under visible light (≥400 nm) illumination. (E)-NAAM microcrystals containing symmetric twinned sealed cavities were prepared using a surfactant-mediated crystal seeded growth method. When exposed to light, the hollow microcrystals exhibited robust photomechanical motions, including bending and dramatic directional expansion of up to 43.1% elongation of the original crystal length before fragmentation due to the photosalient effect. The sealed cavities inside the microcrystals could store different aqueous dye solutions for approximately one month and release the solutions instantly upon light irradiation. A unique slow-fast-slow crystal elongation kinematic process was observed, suggesting significant molecular rearrangements during the illumination period, leading to an average anisotropic crystal elongation of 37.0% (±3.8%). The significant molecular structure and geometry changes accompanying the photocycloaddition reaction, which propels photochemistry to nearly 100% completion, also facilitate photomechanical crystal expansion. Our results provide a possible way to rationally design molecular structures and engineer crystal morphologies to promote more interesting photomechanical behaviors.