Accurate density functional theory description of binding constants and NMR chemical shifts of weakly interacting complexes of C₆₀ with corannulene-based molecular bowls

Abstract

Density functional calculations on "catch and release" complexes of C60 with corannulene derived molecular bowls show that computationally obtained (1) H nuclear magnetic resonance (NMR) chemical shifts can be used as a reliable predictor of binding constants. A wide range of functionals was benchmarked against accurate ab initio calculations to ensure a credible representation of the weak forces that dominate the interactions in these systems. The most reliable density functional theory (DFT) results were then calibrated using experimentally observed NMR data. Careful analysis and comparison of a wide range of commonly used density functionals shows that the explicit inclusion of dispersion corrections is currently the only reliable way to accurately describe the systems investigated in our study. Moreover, we are able to show that the B97-D and ωB97X-D functionals are not only able to reproduce ab initio benchmark calculations, but they do so accurately with a moderately sized basis sets and without the problems of numerical integration we encountered with other functionals in this study.

Adsorption of polycyclic aromatic hydrocarbons and inversion barriers of curved conjugated systems inside the molecular cage ExCage6+

“…Corannulene and sumanene are perhaps the most studied fullerene fragments because they are ideals building block to construct fullerene receptors . One of the most interesting aspects of corannulene is its fast bowl‐to‐bowl inversion .…”

“…Therefore, much work is necessary to replicate the reduction of inversion barriers observed for graphene.buckybowls, density functional theory, supramolecular chemistry 1 | I N TR ODU C TI ON Corannulene and sumanene are perhaps the most studied fullerene fragments [1,2] because they are ideals building block to construct fullerene receptors. [3][4][5][6][7][8][9][10][11][12][13] One of the most interesting aspects of corannulene is its fast bowl-to-bowl inversion. [11][12][13][14] As early as 1992, Scott et al [14] showed that corannulene inverts more than 200 000 times per second at room temperature.…”

Structure and absorption in C60–zinc tetra-phenylporphyrin composite materials: A computational study

“…The proximity of the Zn atom to the C60 C=C suggests that some formal bonding character may exist between the ZnTPP and the C60 cage. However, this is not the case, and we conclude that the main factor binding the two fragments remains π-π stacking, as is the case for related (non-porphyrin) fullerene complexes [34]. Supplementary ONIOM calculations using the BP86 functional [38,39] instead of M06-2X for the high-level reveal the importance of describing non-bonding interactions, such as the π-π stacking, in C60 composite materials.…”

“…functional [33] in conjunction with the 6-31G(d,p) basis set as the high level method, due to its ability in describing non-bonding and π-π interactions. A recent investigation [34] [36] provided the most accurate excitation energies compared to a number of other functionals.…”

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

“…The specific π…π interactions between two compounds are responsible for columnar packing in the crystal structure. 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 …”