▎ 摘　　要

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 that is grossly overlooked in the literature. For totally nonpassivated antidots, in contrast to the fully passivated ones, we show that the resulting CIRCO aromaticity pattern is dominated by s aromaticity rooted in the dangling bonds of the antidots, which is of the Clar type, even though Clars rules were devised for common p aromaticity. On the other hand, the p aromaticity of the fully passivated antidots, the ones commonly studied in the literature, is very much determined by the aromaticity pattern of the parent structure. Thus, the overall aromatic and electronic characteristics of fully passivated finite antidot-decorated nanographenes, similarly to those of the intact nanographenes, are practically determined from the aromaticity pattern of the intact parent nanographene, which, as we illustrated earlier, shows a three-member periodicity in which most of the known periodicities in the properties of nanographenes, nanoribbons, and nanotubes are rooted. It is concluded, therefore, that most or all of the rules for gap opening based on aromaticity and/or chirality in reality stem from these aromatic periodicities.