Abstract
Stacking interactions between substituted buckybowls (corannulene and sumanene) with fullerenes (C60 and C70) were studied at the B97-D2/TZVP level. Corannulene and sumanene monomers were substituted with five and six Br, Cl, CH3, C2H or CN units, respectively. This work was carried out for supplement our previous work of the study of substituent effects in corannulene dimers, in which C60-like (‘fullerene copy’, corannulene with curvature of buckminsterfullerene, C60) was employed to imitate the concave-convex interactions between substituted corannulenes and fullerene C60. Despite the promising results using C60-like, different trends of effects of substituent were obtained for our later calculations using C60. So, C60-like, does not seem representative for imitate the concave-convex interactions between substituted corannulenes and C60. The calculations with fullerenes indicate that all substituents provide a substantial increase of the interaction energy compared with unsubstituted buckybowls, as observed previously. However, substitution with CH3 groups is more favorable than substitution with CN groups, obtained using C60-like. Sumanene substituted with six CH3 groups caused the largest effect increasing the interaction energy about 11 kcal.mol-1 compared with unsubstituted corannulene for both fullerenes. CH-π interactions seem the great responsible for this increase. Stacking interactions between buckybowls evaluated and fullerene C70 show interaction energies quite similar to that obtained with C60. Therefore, it is not expected that buckybowls evaluated to specifically bind one of the fullerenes when exposed to the C60/C70 mixture.
Highlights
The search for molecular receptors for fullerenes is a very attractive field of research in the last years.[1]
A series of complexes composed by substituted buckybowls with fullerenes (C60 and C70) were evaluated at the B97-D2/TZVP level
It is not expected that buckybowls evaluated to bind one of the fullerenes when exposed to the C60/C70 mixture
Summary
The search for molecular receptors for fullerenes is a very attractive field of research in the last years.[1] Several compounds have been explored in pursuit of more effective and selective fullerene receptors.[2,3,4,5,6,7,8] A promising strategy to design new molecular receptors for fullerenes is to use the concave-convex complementarity In this context, the curved polynuclear aromatic hydrocarbons, known as buckybowls or fullerene fragments, seem ideal candidates given that the concave surface of one buckybowl can fits highly to the convex surface of the fullerenes by concave-convex ‘ball-and-socket’ interactions.[4]. The association constants obtained were relatively small and highly dependent of substituents, so that one could argue that the true interaction that bound the complex was that taking place between the fullerene and the edge substituents of corannulene and not the !!!!! interaction between corannulene and fullerene
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