Intramolecular Chalcogen Bonding Activated SuFEx Click Chemistry for Efficient Organic-Inorganic Linking

Abstract

Abstract SuFEx click chemistry demonstrates remarkable molecular assembly capabilities. However, the effective utilization of alkyl sulfonyl fluoride hubs in SuFEx chemistry, particularly in reactions with alcohols and primary amines, presents considerable challenges. In this study, we pioneered an intramolecular chalcogen bonding activated SuFEx (S-SuFEx) click chemistry employing alkyl sulfonyl fluorides with γ-S as the activating group. The chalcogen bonding activated alkyl sulfonyl fluorides can react smoothly with phenols, alcohols, and amines, exhibiting superior reactivity compared to SO2F2. Excellent yields were achieved with all 74 tested substrates. Alkyl sulfonyl fluorides featuring γ-S can be effectively synthesized via the thiol-ene reaction between thiols and ethenesulfonyl fluoride (ESF), which equips S-SuFEx chemistry with the potent capability to link thiols and O, N-nucleophiles using ESF as the linker. Pioneering the application of S-SuFEx chemistry, we highlight its immense potential in organic-inorganic linking, considering the critical role of interfacial covalent bonding in material fabrication. The S-SuFEx hub 1c, incorporating a trialkoxy silane group was specifically designed and synthesized for organic-inorganic linking. We have demonstrated that, in a simple step, 1c efficiently anchors various organic compounds onto surfaces of inorganic materials, leading to the formation of functionalized surfaces with properties such as antibacterial activity, hydrophobicity, and fluorescence.