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Understanding the Reactivity of Ion-Encapsulated Fullerenes

The influence of the encapsulation of an ion inside the C 60 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@C 60 (M=Li + , Na + , K + , Be 2+ , Mg 2+ , Al 3+ , and Cl − ) was studied and compared to the analogous process involving the parent C 60 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 C 60 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

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.

© Chemistry - A European Journal, 2017, vol. 23, núm. 46, p. 11030-11036

Wiley

Manager: Ministerio de Economía y Competitividad (Espanya)
Author: García-Rodeja, Yago
Solà i Puig, Miquel
Bickelhaupt, F. Matthias
Fenández López, Israel
Date: 2017 August 16
Abstract: The influence of the encapsulation of an ion inside the C 60 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@C 60 (M=Li + , Na + , K + , Be 2+ , Mg 2+ , Al 3+ , and Cl − ) was studied and compared to the analogous process involving the parent C 60 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 C 60 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
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.
Format: application/pdf
Citation: https://doi.org/10.1002/chem.201701506
ISSN: 0947-6539 (versió paper)
1521-3765 (versió electrònica)
Document access: http://hdl.handle.net/10256/14360
Language: eng
Publisher: Wiley
Collection: MINECO/PE 2015-2017/CTQ2014-54306-P
Versió postprint del document publicat a: 10.1002/chem.201701506
Articles publicats (D-Q)
Is part of: © Chemistry - A European Journal, 2017, vol. 23, núm. 46, p. 11030-11036
Rights: Tots els drets reservats
Subject: Ful·lerens
Fullerenes
Funcional de densitat, Teoria del
Density functionals
Reaccions d’addició
Addition reactions
Title: Understanding the Reactivity of Ion-Encapsulated Fullerenes
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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