Journal Article

Controllable multiple-step configuration transformations in a thermal/photoinduced reaction

Braunstein, Pierre, Lang, Jian-Ping, Hu, Fei-Long, Hirao, Hajime, Mi, Yan, Wang, Meng-Fan, Niu, Zheng

2022

Overview

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. Solid-state photochemical reactions of olefinic compounds provide access to organic cyclic molecules with specific configurations but the precise control of the stereochemistry in these reactions remains challenging. Here, the authors demonstrate control of the regiospecific configurations of C=C groups and the intermediates by varying temperatures in multi-step thermal and photoinduced ring opening and closing reactions using a single-crystal coordination polymer platform.

• Publisher: Nature Publishing Group UK,Nature Publishing Group,Nature Portfolio
• Subject: 639/638/263/915 / 639/638/298/923/3931 / 639/638/439/890 / Configurations / Coordination polymers / Crystals / Density functional theory / Functional groups / Humanities and Social Sciences / Infrared spectroscopy / Intermediates / Macromolecules / multidisciplinary / Photochemical reactions / Photochemicals / Polymers / Ring opening / Science / Science (multidisciplinary) / Single crystals / Solid state / Stereochemistry / Thermal transformations / X ray powder diffraction / X-ray diffraction