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Theoretical Study on the Diels–Alder Reaction of Fullerenes: Analysis of Isomerism, Aromaticity, and Solvation

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Centro de Investigação em Química da Universidade do Porto, Department of Chemistry and Biochemistry, Faculty of Science, Institute of Molecular Sciences (IMS), University of Porto, Rua do Campo Alegre, P4169-007 Porto, Portugal
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Laboratório Associado para a Química Verde-REQUIMTE, Department of Chemistry and Biochemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, P4169-007 Porto, Portugal
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Author to whom correspondence should be addressed.
Academic Editor: Edward Lee-Ruff
Organics 2022, 3(4), 364-379; https://doi.org/10.3390/org3040025
Received: 6 August 2022 / Revised: 9 September 2022 / Accepted: 19 September 2022 / Published: 22 September 2022
(This article belongs to the Collection Advanced Research Papers in Organics)
Fullerenes are reactive as dienophiles in Diels–Alder reactions. Their distinctive molecular shape and properties result in interesting and sometimes elusive reaction patterns. Herein, to contribute to the understanding of fullerene reactivity, we evaluate the energies of reactions for Diels–Alder cycloadditions of C60, C70, and IC60MA with anthracene (Ant), by means of DFT computational analysis in vacuum and solution. The methods used showed little differentiation between the reactivity of the different fullerenes. The C70-Ant adducts where addition takes place near the edge of the fullerene were found to be the most stable regioisomers. For the IC60MA-Ant adducts, the calculated energies of reaction increase in the order: equatorial > trans-3 > trans-2 ≈ trans-4 ≈ trans-1 > cis-3 > cis-2. The change in the functional suggests the existence of stabilizing dispersive interactions between the surface of the fullerene and the addends. HOMA (harmonic oscillator model of aromaticity) analysis indicated an increase in aromaticity in the fullerene hexagons adjacent to the bonded addend. This increase is bigger in the rings of bisadduct isomers that are simultaneously adjacent to both addends, which helps explain the extra stability of the equatorial isomers. Solvation by m-xylene decreases the exothermicity of the reactions studied but has little distinguishing effect on the possible isomers. Thermal corrections reduce the exothermicity of the reactions by ~10 kJ∙mol−1. View Full-Text
Keywords: fullerenes; ICMA; cycloaddition; regioisomers; DFT fullerenes; ICMA; cycloaddition; regioisomers; DFT
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MDPI and ACS Style

Rodrigues, D.J.L.; Santos, L.M.N.B.F.; Melo, A.; Lima, C.F.R.A.C. Theoretical Study on the Diels–Alder Reaction of Fullerenes: Analysis of Isomerism, Aromaticity, and Solvation. Organics 2022, 3, 364-379. https://doi.org/10.3390/org3040025

AMA Style

Rodrigues DJL, Santos LMNBF, Melo A, Lima CFRAC. Theoretical Study on the Diels–Alder Reaction of Fullerenes: Analysis of Isomerism, Aromaticity, and Solvation. Organics. 2022; 3(4):364-379. https://doi.org/10.3390/org3040025

Chicago/Turabian Style

Rodrigues, Diogo J. L., Luís M. N. B. F. Santos, André Melo, and Carlos F. R. A. C. Lima. 2022. "Theoretical Study on the Diels–Alder Reaction of Fullerenes: Analysis of Isomerism, Aromaticity, and Solvation" Organics 3, no. 4: 364-379. https://doi.org/10.3390/org3040025

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