Controllable multiple-step configuration transformations in a thermal/photoinduced reaction
Meng-Fan Wang 1, Yan Mi 2, Fei-Long Hu 2,*（胡飞龙）, Hajime Hirao 3,*, Zheng Niu 1,*（牛政）, Pierre Braunstein4 &Jian-Ping Lang 1,*（郎建平）
1 College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu, People’s Republic of China
2 Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, Guangxi University for Nationalities, Nanning, Guangxi, People’s Republic of China
3 School of Life and Health Sciences, The Chinese University of Hong Kong, Shenzhen, Longgang Dist., Shenzhen, Guangdong, People’s Republic of China
4 Université de Strasbourg - CNRS, Institut de Chimie (UMR 7177 CNRS), Strasbourg, France
NATURE COMMUNICATIONS，(2022) 13:2847
Solid-state photochemical reactions of olefinic compounds have been demonstrated to represent powerful access to organic cyclic molecules with specific configurations. However, the precise control of the stereochemistry in these reactions remains challenging owing to complex and fleeting configuration transformations. Herein, we report a unique approach to control the regiospecific configurations of C = C groups and the intermediates by varying temperatures in multiple-step thermal/photoinduced reactions, thus successfully realizing reversible ring closing/opening changes using a single-crystal coordination polymer platform. All stereochemical transitions are observed by in situ single-crystal X-ray diffraction, powder X-ray diffraction and infrared spectroscopy. Density functional theory calculations allow us to rationalize the mechanism of the synergistic thermal/photoinduced transformations. This approach can be generalized to the analysis of the possible configuration transformations of functional groups and intermediates and unravel the detailed mechanism for any inorganic, organic and macromolecular reactions susceptible to incorporation into single-crystal coordination polymer platforms.