Modeling the Inversion of Buckybowls on Graphynes for Shape-Complementary Catalysis

Given the ubiquity of surface characterization techniques in recent years, shape-complementary catalysis that induces molecular reorganization on surfaces has attracted significant attention. Herein, we investigate the bowl-to-bowl inversion of buckybowls (corannulene, acecorannulylene, semibuckminsterfullerene, and acenaphtho[3,2,1,8-cdefg]benzo[5,6]-as-indaceno[3,2,1,8,7-mnopqr]chrysene (TWB)) adsorbed on graphene and γ-graphyne (γ-GY) membranes using atomistic potential modeling. The inversion profiles are characterized using the nudged elastic band approach, wherein intramolecular interactions are modeled using the COMPASS force field, and intermolecular interactions are described by an improved Lennard–Jones potential. The extent of shape-complementary catalysis is largely governed by the strength of the van der Waals interactions between the buckybowls and the substrates. Notably, the inversion barrier of corannulene is reduced from 9.2 kcal/mol in the gas phase to 5.86, 7.34, and 7.70 kcal/mol when bound to graphene, γ-GY-1, and γ-GY-2, respectively. For TWB, the inversion barrier follows the same trend and decreases from 122.65 to 101.33 kcal/mol upon graphene binding. The catalytic effectiveness of the investigated carbon membranes is governed by their carbon densities (graphene > γ-GY-1 > γ-GY-2). However, in the case of semibuckminsterfullerene, the porous nature of γ-GYs plays an important role in catalytic activity via partial accommodation of the twisted architecture of intermediate and transition states, resulting in a 35% reduction in the inversion barrier in γ-GY-2, highlighting porosity as a design parameter in shape-complementary catalysis. Our empirical methodology, validated against density functional theory for selected systems, offers a computationally efficient alternative to electronic structure methods for capturing inversion kinetics. These findings highlight the potential of GYs as tunable catalysts for molecular rearrangements and provide a practical framework for assessing surface-mediated catalysis.