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Nature of C60 and C70 fullerene encapsulation in a porphyrin- and metalloporphyrin-based cage: Insights from dispersion-corrected density functional theory calculations

dc.contributor.authorCamacho Gonzalez J.
dc.contributor.authorMondal S.
dc.contributor.authorOcayo F.
dc.contributor.authorGuajardo-Maturana R.
dc.contributor.authorMuñoz-Castro A.
dc.date.accessioned2020-09-02T22:14:16Z
dc.date.available2020-09-02T22:14:16Z
dc.date.issued2020
dc.identifier10.1002/qua.26080
dc.identifier.citation120, 3, -
dc.identifier.issn00207608
dc.identifier.urihttps://hdl.handle.net/20.500.12728/3937
dc.descriptionThe search for efficient synthetic hosts able to encapsulate fullerenes has attracted attention with regard to the purification and formation of ordered supramolecular architectures. This study of a porphyrin-based cage as an extension of the well-described ExCage6+ and BlueCage6+, involving viologen as sidearms, provides an interesting scenario where the oblate C70 fullerene is preferred in comparison to the spherical C60. Our results expose the nature of the fullerene-cage interaction involving ∼50% of dispersion-type interactions evidencing the strong π⋯π surface stacking, with a complementary contribution by the electrostatic and orbital polarization character produced by a charge reorganization with a charge accumulation facing the porphyrin macrocycles and a charge depletion along the equator formed by the viologens sidearms. Interestingly, the central N4H2 ring from each porphyrin contributes to the dispersion term via N-H⋯π interactions, which is decreased when the metallate N4Zn is evaluated. Thus, the formation of stable and selective fullerene encapsulation can be achieved by taking into account two main driving forces, namely, (a) the extension of the π⋯π and X-H⋯π stacking surface and (b) charge reorganization over the fullerene surfaces, which can be used to control fine tuning of the encapsulation thanks to the introduction of more electron-deficient and electron-rich groups within the host cage. © 2019 Wiley Periodicals, Inc.
dc.language.isoen
dc.publisherJohn Wiley and Sons Inc.
dc.subjectfullerenes
dc.subjecthost-guest
dc.subjectnon-covalent interactions
dc.subjectporphyrin
dc.subjectDispersions
dc.subjectFullerenes
dc.subjectPorphyrins
dc.subjectZinc compounds
dc.subjectCharge accumulation
dc.subjectDispersion-corrected density functional
dc.subjectFullerene encapsulation
dc.subjectFullerene surfaces
dc.subjectHost-guests
dc.subjectNon-covalent
dc.subjectOrbital polarizations
dc.subjectSupramolecular architectures
dc.subjectDensity functional theory
dc.titleNature of C60 and C70 fullerene encapsulation in a porphyrin- and metalloporphyrin-based cage: Insights from dispersion-corrected density functional theory calculations
dc.typeArticle


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