A Supramolecular Catalyst for Selective Photo-oxidation with Catalytic Amount Enabled by Activating Substrates into Radicals

Open AccessCCS ChemistryRESEARCH ARTICLES15 Jan 2025A Supramolecular Catalyst for Selective Photo-oxidation with Catalytic Amount Enabled by Activating Substrates into Radicals Xingchen Tang, Junrui Qin, Weiquan Xu, Jiang-Fei Xu and Xi Zhang Xingchen Tang , Junrui Qin , Weiquan Xu , Jiang-Fei Xu and Xi Zhang https://doi.org/10.31635/ccschem.025.202405229 SectionsSupplemental MaterialAboutPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Supramolecular catalysis based on macrocyclic hosts can enhance the reaction rate and selectivity by leveraging their steric hindrance or nano-confinement effects. Herein, we propose an enzyme-like supramolecular catalytic system by combining the nanocavity of cucurbit[8]uril with the photoactivation ability of photoinduced electron transfer, in order to effectively activate substrates into reactive intermediates. The supramolecular catalyst, a host-guest complex of cucurbit[8]uril and a viologen derivative, recognized and activated benzyl alcohol substrates into reactive ketyl radicals through the host-promoted photoinduced electron transfer process. In the meantime, the generation of oxidant O2•− was also enhanced. As a result, the photo-oxidation of benzyl alcohol to aldehyde was greatly facilitated with remarkable yield (90~99%) for substrates with varied substituents and molecular backbones. The benzyl aldehyde products could be replaced by benzyl alcohol substrates from supramolecular catalysts due to their reduced binding affinity, contributing to a highly efficient catalytic cycle. Interestingly, owing to the activation of benzyl alcohol moiety, an unusual preference for oxidizing hydroxyl groups over sulfide groups could be realized. This supramolecular catalytic system demonstrates superior efficiency and selectivity, offering a facile yet effective design strategy for supramolecular catalysis and expanding the toolkit for photocatalysis. Download figure Download PowerPoint Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentNot Yet AssignedSupporting Information Copyright & Permissions© 2025 Chinese Chemical Society Downloaded 0 times PDF downloadLoading ...