Nature of C60 and C70 fullerene encapsulation in a porphyrin- and metalloporphyrin-based cage: Insights from dispersion-corrected density functional theory calculations
Author
dc.contributor.author
Camacho González, Johanna
Author
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Mondal, Sukanta
Author
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Ocayo, Fernanda
Author
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Guajardo Maturana, Raúl
Author
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Muñoz Castro, Alvaro
Admission date
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2022-12-27T13:59:40Z
Available date
dc.date.available
2022-12-27T13:59:40Z
Publication date
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2020
Cita de ítem
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International Journal of Quantum Chemistry Volume120, Issue 3 February 5, 2020 e26080
Identifier
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1097461X
Identifier
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00207608
Identifier
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10.1002/qua.26080
Identifier
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https://repositorio.uchile.cl/handle/2250/190613
Abstract
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The 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.
Patrocinador
dc.description.sponsorship
Fondo Nacional de Desarrollo Científico y Tecnológico, Grant/Award Number: 1180683; University Grants Commission, Grant/Award Number: F.30-458/2019(BSR)
Nature of C60 and C70 fullerene encapsulation in a porphyrin- and metalloporphyrin-based cage: Insights from dispersion-corrected density functional theory calculations