Is Antidot-Patterned Graphene Aromatic? Unusual Aromatic Properties of Graphene Antidot Lattices and Antidot-Functionalized Nanographenes

Abstract

On the basis of our recent predictions for a coupled resonance aromaticity pattern of graphene (J. Phys. Chem. C 2015, 119, 16991), we have studied the anticipated breaking or uncoupling of such dual patterns induced by the presence of particular antidots arranged periodically in a graphene or nanographene film, using numerous properly selected microscopic real-space models in the framework of ab initio density functional theory (DFT). We found that the aromaticity pattern of the antidots is literally tuned to the Clar-type primary aromaticity pattern of graphene, generated by repeated motifs of the hexagonal circumcoronene (CIRCO) pattern, in such a way that the centers of the CIRCO motifs coincide with the centers of the antidots. Thus, the aromaticity pattern of the antidot lattice consists of the isolated primary CIRCO pattern of graphene. However, the nature of the aromaticity and the related bonding and banding characteristics are largely dependent on the degree of antidot passivation, a subject tha...