Understanding the Reactivity of Ion‐Encapsulated Fullerenes

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 ana...

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Bibliographic Details
Published in:Chemistry : a European journal 2017-08, Vol.23 (46), p.11030-11036
Main Authors: García‐Rodeja, Yago, Solà, Miquel, Bickelhaupt, F. Matthias, Fernández, Israel
Format: Article
Language:English
Subjects:
Activation analysis
Activation energy
Addition reactions
Aluminum
Buckminsterfullerene
Cages
cations
Chloride
cycloaddition
Decomposition reactions
density functional calculations
Density functionals
Encapsulation
Energy consumption
Fullerenes
Ful·lerens
Funcional de densitat, Teoria del
Magnesium
Reaccions d'addició
Reactivity
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Summary: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. Tuning fullerene reactivity: The encapsulation of an ion inside the C60 fullerene cage has a tremendous impact on the exohedral reactivity of the C60 moiety. The origins of the observed reactivity trend (see figure) was quantitatively explored in detail by means of density functional calculations.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201701506