In situ observation of a stepwise [2 + 2] photocycloaddition process using fluorescence spectroscopy

• Published in: Nature communications Vol. 14; no. 1; p. 7766
• Main Authors: Wang, Meng-Fan, Deng, Yun-Hu, Hong, Yu-Xuan, Gu, Jia-Hui, Cao, Yong-Yong, Liu, Qi, Braunstein, Pierre, Lang, Jian-Ping
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 27.11.2023; Nature Publishing Group; Nature Portfolio
• Subjects: 119/118; 140/125; 639/301/923/3931; 639/638/263/915; 639/638/439/890; Blue shift; Coordination polymers; Crystals; Evolution; Fluorescence; Fluorescence spectroscopy; Humanities and Social Sciences; Inhomogeneity; Intermediates; Irradiation; Light irradiation; Luminous intensity; multidisciplinary; Polymers; Reaction mechanisms; Science; Science (multidisciplinary); Single crystals; Solid state; Spectroscopy; Spectrum analysis; Ultraviolet radiation
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-023-42604-9

Using highly sensitive and selective in situ techniques to investigate the dynamics of intermediates formation is key to better understand reaction mechanisms. However, investigating the early stages of solid-state reactions/transformations is still challenging. Here we introduce in situ fluorescence spectroscopy to observe the evolution of intermediates during a two-step [2 + 2] photocycloaddition process in a coordination polymer platform. The structural changes and kinetics of each step under ultraviolet light irradiation versus time are accompanied by the gradual increase-decrease of intensity and blue-shift of the fluorescence spectra from the crystals. Monitoring the fluorescence behavior using a laser scanning confocal microscope can directly visualize the inhomogeneity of the photocycloaddition reaction in a single crystal. Theoretical calculations allow us to rationalize the fluorescence behavior of these compounds. We provide a convenient strategy for visualizing the solid-state photocycloaddition dynamics using fluorescence spectroscopy and open an avenue for kinetic studies of a variety of fast reactions. Using highly sensitive and selective in situ techniques to investigate the dynamics of intermediates formation is key to better understand reaction mechanisms but investigating the early stages of solid-state reactions or transformations is still challenging. Here the authors use in situ fluorescence spectroscopy to observe the evolution of intermediates during a two-step [2 + 2] photocycloaddition process in a coordination polymer.