Photoswitchable dynamic conjugate addition-elimination reactions as a tool for light-mediated click and clip chemistry

• Published in: Nature communications Vol. 14; no. 1; pp. 4015 - 11
• Main Authors: Lu, Hanwei, Ye, Hebo, Zhang, Meilan, Liu, Zimu, Zou, Hanxun, You, Lei
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 07.07.2023; Nature Publishing Group; Nature Portfolio
• Subjects: 639/638/403/934; 639/638/541/962; Amines; Assemblies; Chemical bonds; Chemical reactions; Chemistry; Click Chemistry; Conjugates; Covalence; Covalent bonds; Humanities and Social Sciences; Intermediates; Light; multidisciplinary; Nucleophiles; Polymers; Science; Science (multidisciplinary); Smart materials; Solid surfaces; Sulfhydryl Compounds
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-023-39669-x

Phototriggered click and clip reactions can endow chemical processes with high spatiotemporal resolution and sustainability, but are challenging with a limited scope. Herein we report photoswitchable reversible covalent conjugate addition-elimination reactions toward light-addressed modular covalent connection and disconnection. By coupling between photochromic dithienylethene switch and Michael acceptors, the reactivity of Michael reactions was tuned through closed-ring and open-ring forms of dithienylethene, allowing switching on and off dynamic exchange of a wide scope of thiol and amine nucleophiles. The breaking of antiaromaticity in transition states and enol intermediates of addition-elimination reactions provides the driving force for photoinduced change in kinetic barriers. To showcase the versatile application, light-mediated modification of solid surfaces, regulation of amphiphilic assemblies, and creation/degradation of covalent polymers on demand were achieved. The manipulation of dynamic click/clip reactions with light should set the stage for future endeavors, including responsive assemblies, biological delivery, and intelligent materials. Photoinduced dynamic covalent bonds have the advantage of light-mediated bond making and breaking. Here, the authors report photoswitchable dynamic conjugate addition-elimination reactions with a broad scope and demonstrate diverse applications.