Substituted Corannulenes and Sumanenes as Fullerene Receptors. A Dispersion-Corrected Density Functional Theory Study

Abstract

Stacking interactions between substituted buckybowls (corannulene and sumanene) with fullerenes (C60 and C70) were studied at the B97-D2/TZVP level of theory. Corannulene and sumanene monomers were substituted with five and six Br, Cl, CH3, C2H, or CN units, respectively. A comprehensive study was conducted, analyzing the interaction of corannulenes and sumanenes with several faces of both fullerenes. According to our results, in all cases substitution gave rise to larger interaction energies if compared with those of unsubstituted buckybowls. The increase of dispersion seems to be the main source of the enhanced binding, so an excellent correlation between the increase of interaction energy and the increase of dispersion contribution takes place. One of the noteworthy phenomena that appears is the so-called CH···π interaction, which is responsible for the strong interaction of sumanene complexes (if compared with that of corannulene complexes). This interaction also causes the substitution with CH3 groups (in which one of the H atoms points directly to the π cloud of fullerene) to be the most favorable case. This fact can be easily visualized by noncovalent interaction plots.

Assembling Nonplanar Polyaromatic Units by Click Chemistry. Study of Multicorannulene Systems as Host for Fullerenes

“…The value for 3⊂C 60 (−44.26 kcal/mol) is near twice as much as those formed by C 60 and a single penta-substituted corannulene reported by Rodríguez-Otero et al (≈-22 kcal/mol) 17 and very similar to that obtained by Sygula and co-workers in their buckycatcher (−43.1 kcal/ mol). 5e This expected result confirms that both corannulene subunits contribute equally to stabilize this adduct.…”

“…17 This result is in agreement with the fact that the major contribution to the interaction energy is the π−π interaction between a corannulene and a C 60 . Because in our host with three corannulenes (compound 2) the spacer is not long enough to allow the three corannulenes to interact with C 60 , an association constant similar to that of the host with only two corannulenes (compound 3) was obtained.…”

Review of Experimental GAPT and Infrared Atomic Charges in Molecules

“…For example, a theoretical study of the stacking interaction between substituted buckybowls and fullerenes showed that only dispersion-corrected functionals such as B97-D2 are able to predict its stabilization. 89 Another study on the stability of a charged porphyrin derivative showed that dispersion is necessary to compensate its strong electrostatic repulsion and stability is only found through dispersion-corrected functionals like B3LYP-D3. 90 More work on experimental infrared intensities, polar tensors, GAPT charges and their applications are being carried out in our laboratory…”

How the substituents in corannulene and sumanene derivatives alter their molecular assemblings and charge transport properties?-A theoretical study with a dimer model

“…Otherwise, these special interactions have attracted great attention due to their essential role in understanding the structure‐property relationships and the fascinating photoelectronic properties of these curved compounds . For example, Jesus Rodriuez‐Otero group studied the stacking interactions not only between the substituted corannulenes dimers, but also between the substituted corannulenes/sumanenes and C60/C70 using DFT‐D method; Huang et al also investigated the π…π interaction between curved and planar (C‐P) structures, and revealed the specific photoelectric properties of C‐P complexes …”