AbstractPhotoresponsive smart materials, which exhibit swift or instantaneous responses to external light stimuli, are pivotal for advancing the development of novel smart devices. Among these materials, photoresponsive tetracoordinate arylboron compounds emerge as prominent molecular systems, owing to their captivating photochemical mechanisms and photophysical transformations. In recent years, these molecules have experienced notable progress, leading to the emergence of numerous organic boron photoresponsive molecular systems with innovative structures and exceptional performance. In this comprehensive review, we present a thorough examination of the latest advancements in the field, systematically elucidating the design strategies and structure‐activity relationships of these molecules. Furthermore, we delve into the photoresponse mechanisms of various molecules and summarize their unique characteristics. Ultimately, we analyze the challenges, opportunities, and prospects encountered in this exciting field of research.
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