Regioswitchable Bingel Bis-Functionalization of Fullerene C70 via Supramolecular Masks

Isomer-pure functionalized fullerenes are required to boost the development of fullerene chemistry in any field, but their multiple functionalization renders a mixture of regioisomers that are very difficult to purify by chromatography. For the specific case of C70, its nonspherical geometry makes i...

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Autores: Iannace, Valentina, Sabrià, Clara, Xu, Youzhi, Delius, Max von, Imaz, Inhar, Maspoch, Daniel, Feixas Geronès, Ferran, Ribas Salamaña, Xavi
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2024
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/25058
Acceso en línea:http://hdl.handle.net/10256/25058
Access Level:acceso abierto
Palabra clave:Materials nanoestructurats
Nanostructured materials
Nanotubs de carboni
Carbon nanotubes
Grups funcionals
Functional groups
Ful·lerens
Fullerenes
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spelling Regioswitchable Bingel Bis-Functionalization of Fullerene C70 via Supramolecular MasksIannace, ValentinaSabrià, ClaraXu, YouzhiDelius, Max vonImaz, InharMaspoch, DanielFeixas Geronès, FerranRibas Salamaña, XaviMaterials nanoestructuratsNanostructured materialsNanotubs de carboniCarbon nanotubesGrups funcionalsFunctional groupsFul·lerensFullerenesIsomer-pure functionalized fullerenes are required to boost the development of fullerene chemistry in any field, but their multiple functionalization renders a mixture of regioisomers that are very difficult to purify by chromatography. For the specific case of C70, its nonspherical geometry makes its regioselective functionalization more challenging than that of spherical C60. In this work, the supramolecular mask approach is applied for the first time to C70, which is encapsulated in two different nanocapsules to achieve the Bingel bis-cyclopropanation at α-bonds of opposite poles. Based on the tetragonal prismatic geometry imposed by the smaller supramolecular mask tested, the obtained major bis-adduct is completely reversed (major 5 o’clock) compared to bare C70 functionalization (major 2 o’clock). Moreover, by further restricting the accessibility of C70 using a three-shell Matryoshka mask and dibenzyl-bromomalonate, a single regiospecific 2 o’clock bis-isomer is obtained, owing to the perfect complementarity of the mask and the addend steric properties. The outcome of the reactions is fully explained at the molecular level by means of a thorough molecular dynamics (MD) study of the accessibility of the α-bonds to produce the different bis-adductsThis work was supported by grants from MINECO-Spain (PID2019-104498GB-I00, PID2022-136970NB-I00, and TED2021-130573B-I00 to X.R.; RTI2018-101032-J100, RYC2020-029552-I and PID2022-141676NB-I00 to F.F.), Fundación Areces (RegioSolar project to X.R.), and Generalitat de Catalunya AGAUR (2021SGR00475 and 2021SGR00487). V.I. thanks MINECO for a FPI grant, and C.S. thanks UdG for a Ph.D. grant. We thank the QBIS-CAT research group and STR-UdG for technical support. We also are grateful for the ICREA-Academia award to X.R. M.v.D. acknowledges financial support by the Deutsche Forschungsgemeinschaft (DFG), projektnummer 182849149-SFB953 “Synthetic Carbon Allotropes” (project A7)Open Access funding provided thanks to the CRUE-CSIC agreement with American Chemical Society (ACS)American Chemical Society (ACS)Agencia Estatal de Investigación2024info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionpeer-reviewedapplication/pdfhttp://hdl.handle.net/10256/25058http://hdl.handle.net/10256/25058Journal of the American Chemical Society (JACS), 2024, vol. 146, núm. 8, p. 5186-5194Articles publicats (D-Q)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jacs.3c10808info:eu-repo/semantics/altIdentifier/issn/0002-7863info:eu-repo/semantics/altIdentifier/eissn/1520-5126PID2019-104498GB-I00PID2022-136970NB-I00PID2022-141676NB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-104498GB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-136970NB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-141676NB-I00Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:recercat.cat:10256/250582026-05-29T05:05:01Z
dc.title.none.fl_str_mv Regioswitchable Bingel Bis-Functionalization of Fullerene C70 via Supramolecular Masks
title Regioswitchable Bingel Bis-Functionalization of Fullerene C70 via Supramolecular Masks
spellingShingle Regioswitchable Bingel Bis-Functionalization of Fullerene C70 via Supramolecular Masks
Iannace, Valentina
Materials nanoestructurats
Nanostructured materials
Nanotubs de carboni
Carbon nanotubes
Grups funcionals
Functional groups
Ful·lerens
Fullerenes
title_short Regioswitchable Bingel Bis-Functionalization of Fullerene C70 via Supramolecular Masks
title_full Regioswitchable Bingel Bis-Functionalization of Fullerene C70 via Supramolecular Masks
title_fullStr Regioswitchable Bingel Bis-Functionalization of Fullerene C70 via Supramolecular Masks
title_full_unstemmed Regioswitchable Bingel Bis-Functionalization of Fullerene C70 via Supramolecular Masks
title_sort Regioswitchable Bingel Bis-Functionalization of Fullerene C70 via Supramolecular Masks
dc.creator.none.fl_str_mv Iannace, Valentina
Sabrià, Clara
Xu, Youzhi
Delius, Max von
Imaz, Inhar
Maspoch, Daniel
Feixas Geronès, Ferran
Ribas Salamaña, Xavi
author Iannace, Valentina
author_facet Iannace, Valentina
Sabrià, Clara
Xu, Youzhi
Delius, Max von
Imaz, Inhar
Maspoch, Daniel
Feixas Geronès, Ferran
Ribas Salamaña, Xavi
author_role author
author2 Sabrià, Clara
Xu, Youzhi
Delius, Max von
Imaz, Inhar
Maspoch, Daniel
Feixas Geronès, Ferran
Ribas Salamaña, Xavi
author2_role author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Agencia Estatal de Investigación
dc.subject.none.fl_str_mv Materials nanoestructurats
Nanostructured materials
Nanotubs de carboni
Carbon nanotubes
Grups funcionals
Functional groups
Ful·lerens
Fullerenes
topic Materials nanoestructurats
Nanostructured materials
Nanotubs de carboni
Carbon nanotubes
Grups funcionals
Functional groups
Ful·lerens
Fullerenes
description Isomer-pure functionalized fullerenes are required to boost the development of fullerene chemistry in any field, but their multiple functionalization renders a mixture of regioisomers that are very difficult to purify by chromatography. For the specific case of C70, its nonspherical geometry makes its regioselective functionalization more challenging than that of spherical C60. In this work, the supramolecular mask approach is applied for the first time to C70, which is encapsulated in two different nanocapsules to achieve the Bingel bis-cyclopropanation at α-bonds of opposite poles. Based on the tetragonal prismatic geometry imposed by the smaller supramolecular mask tested, the obtained major bis-adduct is completely reversed (major 5 o’clock) compared to bare C70 functionalization (major 2 o’clock). Moreover, by further restricting the accessibility of C70 using a three-shell Matryoshka mask and dibenzyl-bromomalonate, a single regiospecific 2 o’clock bis-isomer is obtained, owing to the perfect complementarity of the mask and the addend steric properties. The outcome of the reactions is fully explained at the molecular level by means of a thorough molecular dynamics (MD) study of the accessibility of the α-bonds to produce the different bis-adducts
publishDate 2024
dc.date.none.fl_str_mv 2024
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
peer-reviewed
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/25058
http://hdl.handle.net/10256/25058
url http://hdl.handle.net/10256/25058
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/jacs.3c10808
info:eu-repo/semantics/altIdentifier/issn/0002-7863
info:eu-repo/semantics/altIdentifier/eissn/1520-5126
PID2019-104498GB-I00
PID2022-136970NB-I00
PID2022-141676NB-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-104498GB-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-136970NB-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-141676NB-I00
dc.rights.none.fl_str_mv Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society (ACS)
publisher.none.fl_str_mv American Chemical Society (ACS)
dc.source.none.fl_str_mv Journal of the American Chemical Society (JACS), 2024, vol. 146, núm. 8, p. 5186-5194
Articles publicats (D-Q)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,81155

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