Shape Dependence of Photoresponsive Molecular Crystals Composed of Naphthyl Acrylic Acid Stimulated by Solid-State [2 + 2] Photocycloaddition

Author:

Li Tian-Yuan1,Du Yu-Ze1,Xu Tian-Yi1,Zhang Tian-Le1,Tong Fei1ORCID

Affiliation:

1. Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China

Abstract

Photomechanical molecular crystals, actuated by solid-state photochemical reactions, manifest a spectrum of mechanical motions upon light exposure, underscoring their prospective integration into the next generation of intelligent materials and devices. Utilizing the solid-state photodimerization of naphthyl acrylic acid as a paradigm, this study delved into the interplay between crystal morphology and reaction dynamics on the photomechanical responses of molecular crystals. Distinct crystal forms—bulk, microrods, and microplates—were cultivated through tailored crystallization conditions. While bulk crystals of naphthyl acrylic acid (NA) underwent shattering and splintering upon UV light exposure, the microplate counterparts displayed unique cracking patterns with fissures yet retained their overall structural integrity. In contrast, NA microrods underwent pronounced bending under identical irradiation conditions. These phenomena are attributed to the efficient lattice reconfiguration stemming from the [2 + 2] cycloaddition photochemical reaction within the crystals. An intermediate fluorescence enhancement was observed across all crystal types upon light exposure. Collectively, our results underscore the pivotal role of crystal shape in dictating photomechanical behavior, thereby heralding novel strategies for developing advanced photomechanical materials.

Funder

National Natural Science Foundation of China

Science and Technology Commission of Shanghai Municipality

Fundamental Research Funds for the Central Universities

Publisher

MDPI AG

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