Cation–π complexes of a bowl‐shaped polycyclic aromatic hydrocarbon

Ansems, Ronald B. M.; Scott, Lawrence T.

doi:10.1002/poc.800

Cited by 25 publications

(10 citation statements)

References 33 publications

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“…6,[12][13][14] So, for the simplest of these bowls, corannulene, C 20 H 10 , the electrostatic potential is different depending on whether the concave or the convex side of the bowl is considered [12][13][14] and, in fact, cations usually bind corannulene with the convex face. [9][10][11][12][13][15][16][17][18][19][20][21] Anion receptors are of great interest in different chemical and biological applications. [22][23][24] Recently, the possibility of stabilizing interactions between anions and electron-deficient aromatic systems in the so-called anionÁ Á Áp interaction has also aroused interest.…”

Section: Introductionmentioning

confidence: 99%

Interaction between anions and substituted molecular bowls

García-Novo

Campo-Cacharrón

Cabaleiro‐Lago

et al. 2012

Phys. Chem. Chem. Phys.

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Complexes formed by anions and substituted molecular bowls were studied by means of computational methods. The bowls consisted of corannulene molecules substituted with five or ten F, Cl, or CN groups, whereas Cl(-), Br(-) and BF(4)(-) were the anions considered. Substitution with F, Cl and CN hardly affects the geometry of the bowl, but produces an inversion of the molecular electrostatic potential of the bowls, which becomes positive over the two faces of the bowl, therefore interacting favorably with anions. In all cases considered, the most stable complex presents the anion interacting with the concave side of the bowl. The strength of the interaction roughly follows the values of molecular electrostatic potential, being more stable as more positive is the potential. The preference of anions to interact with the concave side of the bowls has its origin in stronger electrostatic and dispersion interactions. Though the solvent produces an important decrease in the stability of the complexes, the results suggest the possibility of employing these substituted buckybowls as anion receptors with a preferential concave complexation, especially for large anions.

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Section: Introductionmentioning

confidence: 99%

Interaction between anions and substituted molecular bowls

García-Novo

Campo-Cacharrón

Cabaleiro‐Lago

et al. 2012

Phys. Chem. Chem. Phys.

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“…The interactions in these concave–convex complexes are unusual because the π orbitals between the curved surfaces are highly polarized, unlike the nearly uniform density of π electrons in graphene sheets 8. As a result, concave carbon surfaces have been calculated to be even better π electron donors than their planar counterparts 9, 10. Recognizing this favorable concave–convex interaction, Sygula et al recently isolated an unconventional complex of C 60 with C 60 H 28 , a “molecular tweezer” with two corannulene subunits11 depicted in Figure 1.…”

Section: Introductionmentioning

confidence: 99%

“…The interactions in these concaveconvex complexes are unusual because the π orbitals between the curved surfaces are highly polarized, unlike the nearly uniform density of π electrons in graphene sheets 8 . As a result, concave carbon surfaces have been calculated to be even better π electron donors than their planar counterparts 9,10 .…”

Section: Introductionmentioning

confidence: 99%

Noncovalent interactions in supramolecular complexes: A study on corannulene and the double concave buckycatcher

Wong

2008

J Comput Chem

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Stimulated by the recent observation of pi-pi interactions between C60 and corannulene subunits in a molecular tweezer arrangement (J Am Chem Soc 2007, 129, 3842), a density functional theory study was performed to analyze the electronic structure and properties of various noncovalent corannulene complexes. The theoretical approach is first applied to corannulene complexes with a series of benchmark molecules (CH4, NH3, and H2O) using several new-generation density functionals. The performance of nine density functionals, illustrated by computing binding energies of the corannulene complexes, demonstrates that Zhao and Truhlar's MPWB1K and M05-2X functionals provide energies similar to that obtained at the SCS-MP2 level. In contrast, most of the other popular density functionals fail to describe this noncovalent interaction or yield purely repulsive interactions. Further investigations with the M05-2X functional show that the binding energy of C60 with corannulene subunits in the relaxed molecular receptor clip geometry is -20.67 kcal/mol. The results of this calculation further support the experimental interpretation of pure pi-pi interactions between a convex fullerene and the concave surfaces of two corannulene subunits.

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“…Going down this series, the curvature of the surface and the depth of the bowl both increase strongly. If the bowl depth is taken as the distance between the basal C 5 plane and the outermost plane of carbons, the bowl depths are as follows: corannulene, 0.89 Å; bowl-30, 2.53 Å; bowl-40, 3.78 Å. Paralleling the development of synthetic access to many compounds of this type − (as well as the related series of bowls having a six-membered ring at the apex and essentially C 3 symmetry), there has been extended interest in their properties and reactivity, − as well as their metal-ion complexes. ,,,− The C 60 fragments with the six-membered ring at the apex ( C 3 ) are apparently easier to access synthetically and have been popular study targets, but for consistency with the corannulene analog, the present study addresses the five-membered-ring ( C 5 ) series. The intense current interest in carbon nanotubes (notably those with curved end caps) and in single-layer graphitic sheets (graphene, as well as curved graphene sheets) lends immediate interest to the interactions of charged particles with conjugated carbon-sheet surfaces.…”

Section: Introductionmentioning

confidence: 99%

When Do Molecular Bowls Encapsulate Metal Cations?

Green

Dunbar

2011

J. Phys. Chem. A

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Curved carbon π surfaces have chemical and physical properties suitable for exploitation for chemical microencapsulation and the self-assembly of nanoscale materials. Advances will greatly benefit from more understanding of their host-guest interactions with guests such as metal cations. Here, quantitative predictions are made for the binding of metal cations to three prototypical surfaces using density functional theory calculations: the buckybowls C(20)H(10), C(30)H(10), and C(40)H(10). The focus was on finding the most favorable binding sites, assessing whether binding is more favorable inside or outside the bowl, and exploring factors influencing the binding site preference. Classes of cations studied included small and large monocations and cations with multiple charges: Na(+), Cs(+), NH(4)(+), Ba(+), Ba(2+), and La(3+). Factors found to favor inside binding were large ion size and high ion charge, suggesting that polarization interactions as well as short-range interactions are important in determining the preferred binding sites inside and outside these buckybowls. Unlike monocations, which at best have only a weak tendency toward encapsulation, the multiply charged cations Ba(2+) and La(3+) were found to have a strong driving force toward containment inside the bowls. Coulomb potentials were found to favor cation binding on the outside surface of the bowls, but cation microsolvation through polarization interactions presents a compensating factor that can tip the balance in favor of encapsulation. Knowledge of these factors will be a valuable tool in the design of nanocontainers and the diverse architecture possible with these structural elements.

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Cation–π complexes of a bowl‐shaped polycyclic aromatic hydrocarbon

Cited by 25 publications

References 33 publications

Interaction between anions and substituted molecular bowls

Interaction between anions and substituted molecular bowls

Noncovalent interactions in supramolecular complexes: A study on corannulene and the double concave buckycatcher

When Do Molecular Bowls Encapsulate Metal Cations?

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