Understanding the Reactivity of Ion-Encapsulated Fullerenes

Yago García-Rodeja; Miquel Solà; F. Matthias Bickelhaupt; Israel Fernández

doi:10.1002/chem.201701506

Understanding the Reactivity of Ion-Encapsulated Fullerenes

Yago García-Rodeja, Miquel Solà, F. Matthias Bickelhaupt, Israel Fernández^*

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

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Abstract

The influence of the encapsulation of an ion inside the C₆₀ fullerene cage on its exohedral reactivity was explored by means of DFT calculations. To this end, the Diels–Alder reaction between 1,3-cyclohexadiene and M@C₆₀ (M=Li⁺, Na⁺, K⁺, Be²⁺, Mg²⁺, Al³⁺, and Cl⁻) was studied and compared to the analogous process involving the parent C₆₀ fullerene. A significant enhancement of the Diels–Alder reactivity is found for systems having an endohedral cation, whereas a clear decrease in reactivity is observed when an anion is encapsulated in the C₆₀ cage. The origins of this reactivity trend were quantitatively analyzed in detail by using the activation strain model of reactivity in combination with energy decomposition analysis.

Original language	English
Pages (from-to)	11030-11036
Number of pages	7
Journal	Chemistry: A European Journal
Volume	23
Issue number	46
Early online date	9 May 2017
DOIs	https://doi.org/10.1002/chem.201701506
Publication status	Published - 16 Aug 2017

Funding

We are grateful for financial support from the Spanish MINECO-FEDER (Grants CTQ2013-44303-P, CTQ2016-78205-P, and CTQ2014-51912-REDC to I. F. and CTQ2014-54306-P to M.S.), the Netherlands Organization for Scientific Research (NWO), and Catalan DIUE (projects 2014SGR931, ICREA Academia 2014 prize, and XRQTC to M.S.). The FEDER grant UNGI10-4E-801 has also funded this research. Y.G.-R. acknowledges the MINECO for a FPI grant.

Funders	Funder number
Catalan DIUE	2014SGR931
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Ministerio de Economía y Competitividad
Institució Catalana de Recerca i Estudis Avançats	UNGI10-4E-801
European Regional Development Fund	CTQ2014-54306-P, CTQ2016-78205-P, CTQ2014-51912-REDC, CTQ2013-44303-P

Keywords

cations
cycloaddition
density functional calculations
fullerenes

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/chem.201701506

Understanding the Reactivity of Ion‐Encapsulated FullerenesFinal published version, 1.52 MBLicence: Article 25fa Dutch Copyright Act

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abstract = "The influence of the encapsulation of an ion inside the C60 fullerene cage on its exohedral reactivity was explored by means of DFT calculations. To this end, the Diels–Alder reaction between 1,3-cyclohexadiene and M@C60 (M=Li+, Na+, K+, Be2+, Mg2+, Al3+, and Cl−) was studied and compared to the analogous process involving the parent C60 fullerene. A significant enhancement of the Diels–Alder reactivity is found for systems having an endohedral cation, whereas a clear decrease in reactivity is observed when an anion is encapsulated in the C60 cage. The origins of this reactivity trend were quantitatively analyzed in detail by using the activation strain model of reactivity in combination with energy decomposition analysis.",

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AU - Fernández, Israel

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Understanding the Reactivity of Ion-Encapsulated Fullerenes

Abstract

Funding

Keywords

UN SDGs

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