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

Complutense University
University of Girona
Vrije Universiteit Amsterdam
Radboud University Nijmegen

Research output: Contribution to journal › Article › peer-review

37 Citations (Scopus)

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
DOIs	https://doi.org/10.1002/chem.201701506
Publication status	Published - 16 Aug 2017
Externally published	Yes

Keywords

cations
cycloaddition
density functional calculations
fullerenes

ASJC Scopus subject areas

Catalysis
Organic Chemistry

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10.1002/chem.201701506

Cite this

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title = "Understanding the Reactivity of Ion-Encapsulated Fullerenes",

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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author = "Yago Garc{\'i}a-Rodeja and Miquel Sol{\`a} and Bickelhaupt, \{F. Matthias\} and Israel Fern{\'a}ndez",

note = "Publisher Copyright: {\textcopyright} 2017 Wiley-VCH Verlag GmbH \& Co. KGaA, Weinheim",

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doi = "10.1002/chem.201701506",

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}

TY - JOUR

T1 - Understanding the Reactivity of Ion-Encapsulated Fullerenes

AU - García-Rodeja, Yago

AU - Solà, Miquel

AU - Bickelhaupt, F. Matthias

AU - Fernández, Israel

PY - 2017/8/16

Y1 - 2017/8/16

N2 - 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.

AB - 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.

KW - cations

KW - cycloaddition

KW - density functional calculations

KW - fullerenes

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JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 46

ER -

Understanding the Reactivity of Ion-Encapsulated Fullerenes

Abstract

Keywords

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