Regioselective access to orthogonal Diels-Alder C60 bis-adducts and tris-heteroadducts via supramolecular mask strategy
dc.contributor.author
dc.date.accessioned
2022-10-06T09:43:35Z
dc.date.available
2022-10-06T09:43:35Z
dc.date.issued
2022-08-17
dc.identifier.uri
dc.description.abstract
The regioselective polyfunctionalization of highly symmetric spherical Ih-C60 is extremely challenging and usually leads to the formation of regioisomeric mixtures not amenable for high-pressure liquid chromatography (HPLC) purification. Here, we pioneer the use of tetragonal prismatic nanocapsules to perform selective Diels-Alder (DA) functionalization of encapsulated Ih-C60 using acenes. The supramolecular mask allows the regioselective synthesis of either e,e-bis-anthracene-C60 (functionalization at 90°) or the synthesis of trans-1-bis-pentacene-C60 (functionalization at 180°) by changing only the acene length. Moreover, the mask strategy allows one to obtain unprecedented equatorial hetero-tris-functionalized-C60 adducts combining Diels-Alder with Bingel mask regiofunctionalization. Computational modeling provides crucial insights to rationalize the regioselective control exerted by the supramolecular mask on the successive DA cycloadditions. Molecular dynamics (MD) simulations revealed significant differences in the host-guest interactions and equilibrium established between the first-formed anthracene- and pentacene-based mono-adducts with the nanocapsule, which finally determine the observed orthogonal regioselectivity
dc.description.sponsorship
This work was supported by grants from MINECO-Spain (PID2019-104498GB-I00 to X.R., PID2019-111300GA-I00 and RYC2020-028628-I to M.G.-B., and PGC2018-095808-B-I00 to T.P.), Fundación Areces (RegioSolar project to X.R.), and Generalitat de Catalunya AGAUR (2017SGR264 to X.R. and H2020 MSCA-Cofund Beatriu de Pinós grant 2018-BP-00204 to M.G.-B)
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Elsevier
dc.relation
PID2019-104498GB-I00
PID2019-111300GA-I00
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Reproducció digital del document publicat a: https://doi.org/10.1016/j.xcrp.2022.100992
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Cell Reports Physical Science, 2022, vol. 3, núm. 8, p. 100992
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Articles publicats (D-Q)
dc.rights
Attribution-NonCommercial-NoDerivatives 4.0 International
dc.rights.uri
dc.subject
dc.title
Regioselective access to orthogonal Diels-Alder C60 bis-adducts and tris-heteroadducts via supramolecular mask strategy
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.relation.projectID
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-104498GB-I00/ES/NANOCAPSULAS COMO PLATAFORMAS SUPRAMOLECULARES PARA LA FUNCIONALIZACION REGIOSELECTIVA DE FULLERENOS Y CATALISIS EN EL ESPACIO CONFINADO/
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-111300GA-I00/ES/CARACTERIZACION MULTIESCALAR DE INTERMEDIOS REACTIVOS PARA EL DESCUBRIMIENTO Y DISEÑO DE NUEVAS ACTIVIDADES BIOCATALITICAS/
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
035654
dc.contributor.funder
dc.type.peerreviewed
peer-reviewed
dc.relation.FundingProgramme
dc.relation.ProjectAcronym
dc.identifier.eissn
2666-3864