Abstract
Corannulene is an unsaturated hydrocarbon composed of fused rings, with one central five-membered ring and five peripheral six-membered rings. Its structure can be considered as a portion of C60. Corannulene is a curved π surface, but unlike C60, it has two accessible different faces: one concave (inside) and one convex (outside). In this work, computational modeling of the binding between alkali metal cations (Li+, Na+, and K+) and corannulene has been performed at the DFT and MP2 levels. Different corannulene···M+ complexes have been studied and the transition states interconnecting local minima were located. The alkali cations can be bound to a five or six membered ring in both faces. At the DFT level, binding to the convex face (outside) is favored relative to the concave face for the three alkali cations studied, as it was previously published. This out preference was found to decrease as cation size increases. At the MP2 level, although a similar trend is found, some different conclusions related to the in/out preference were obtained. According to our results, migration of cations can take place on the convex or on the concave face. Also, there are two ways to transform a concave complex in a convex complex: migration across the edge of corannulene and bowl-to-bowl inversion.
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Notes
With a calculated dipole moment of 2.23 D for corannulene, and taking into account that interaction between a charge a and a dipole b is given by -q a μ b /r 2 if the dipole is aligned with the charge (α = 0), the following energies were obtained: −26, −19, and −15 kcal mol–1 for the interaction between Li+, Na+, and K+, respectively, with the convex side of corannulene. These values show a similar trend to those of Table 2, though as we have shown recently, the interaction is mainly of inductive character rather than electrostatic [15].
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Acknowledgments
This research has been supported by the Xunta de Galicia (project INCITE09209103PR). The authors want to express their gratitude to the CESGA (Centro de Supercomputación de Galicia) for the use of their computers.
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Rellán-Piñeiro, M., Rodríguez-Otero, J., Cabaleiro-Lago, E.M. et al. DFT and MP2 study of the interaction between corannulene and alkali cations. J Mol Model 19, 2049–2055 (2013). https://doi.org/10.1007/s00894-012-1632-8
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DOI: https://doi.org/10.1007/s00894-012-1632-8