Pristine Graphene-Based Catalysis: Significant Reduction of the Inversion Barriers of Adsorbed and Confined Corannulene, Sumanene, and Dibenzo[a,g]corannulene.
Herein, we investigated the inversion of corannulene, sumanene, and dibenzo[a,g]corannulene when they are adsorbed onto graphene or intercalated in bilayer graphene. The results obtained with the M06-L, M06-2X, TPPS-D3, TPSS-D3BJ, B3LYP-D3, and B3LYP-D3BJ methods supported a significant reduction of the inversion barriers. In the case of corannulene adsorbed onto graphene, nonbonded interactions reduce the inversion barrier by at least a 50% with respect to the gas phase, whereas for adsorbed sumanene and dibenzo[a,g]corannulene the reductions are at least 39 and 67%, respectively. When the molecules are intercalated in bilayer graphene the lowering of the activation energy is more significant. In the particular case of dibenzo[a,g]corannulene the molecule is expected to display an almost planar structure, with its 0.83 Å bowl depth almost completely quenched. For intercalated corannulene and sumanene, the inversion barriers are at least 66 and 60% lower, respectively. It is our hope that these results can help to improve the design of receptors that can catalyze the inversion of buckybowls.
Computational Nanotechnology, DETEMA, Facultad de Química, UDELAR, CC 1157, 11800 Montevideo, Uruguay, Montevideo, Uruguay.
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