Supramolecular Mask Regio-Converter: Orthogonal Diels-Alder C 70 Bis-Adducts by Mask-Mediated Regioselective Synthesis

Open AccessCCS ChemistryRESEARCH ARTICLES8 Nov 2024Supramolecular Mask Regio-Converter: Orthogonal Diels-Alder C70 Bis-Adducts by Mask-Mediated Regioselective Synthesis Tània Pèlachs, Clara Sabrià, Valentina Iannace, Inhar Imaz, Felipe Gándara, Daniel Maspoch, Ferran Feixas and Xavi Ribas Tània Pèlachs , Clara Sabrià , Valentina Iannace , Inhar Imaz , Felipe Gándara , Daniel Maspoch , Ferran Feixas and Xavi Ribas https://doi.org/10.31635/ccschem.024.202405057 SectionsSupplemental MaterialAboutPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Pure bis-regioisomers of fullerenes are highly desired due to their potential applications in solar cell devices. The use of nanocapsules as supramolecular masks has proved successful in achieving regioselective Bingel cyclopropanation of C70 to obtain 2 o'clock or 5 o'clock bis-adducts. Here, we extend the mask strategy to Diels-Alder (DA) cycloaddition of C70 with acenes, showing a regiodivergent outcome depending on the length of the diene. The reaction of C70Ì 4 (BArF)8 with anthracene (An) yields 12 o'clock An2-C70Ì 4(BArF)8 as the major species (>90% bis-adduct ratio). Its crystal structure reveals the tight fitting of the An moieties at contiguous windows of the tetragonal prismatic nanocapsule. In contrast, when the larger pentacene (Pn) is used, the reaction selectively affords the 5 o'clock Pn2-C70 (>96% bis-adduct ratio). Molecular dynamics studies show that the mask blocks the formation of the 2 o'clock isomer in both cases and optimizes the regioselective formation of 12 o'clock An2-C70 or 5 o'clock Pn2-C70. Finally, by taking advantage of the different degrees of background retro-DA, the mask is used as a supramolecular regio-converter, fully transforming mixtures of 2 o'clock and 5 o'clock bis-An2-C70 into 12 o'clock bis-An2-C70. Moreover, the mask also completely regioconverts 12 o'clock An2-C70 into 5 o'clock Pn2-C70. Download figure Download PowerPoint Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentNot Yet AssignedSupporting Information Copyright & Permissions© 2024 Chinese Chemical Society Downloaded 0 times PDF downloadLoading ...