Buckybowl is an open geodesic polyaromatic molecule with unevenly distributed π-electron on its convex and concave surface, which leads to a... Show moreBuckybowl is an open geodesic polyaromatic molecule with unevenly distributed π-electron on its convex and concave surface, which leads to a readily accessible π-surface for substitution reactions and complexation with various metals. Despite the diverse structures of buckybowl complexes observed in the previous experimental study, our computational work has shown that the π-surface of buckybowl always plays the most important role in the bonding. Modification of the π-surface by changing the size of conjugation and the curvature enable us to tune the bonding preference of the buckybowl surface and the stability of the complex. Our continued study has shown similar importance of the π-surface in functionalization of buckybowl with different electrophilic groups. Surprisingly, our investigation on buckybowl cations intrigued an original perspective of aromatic behavior of the π-surface. Our results have revealed an intrinsic nature of aromatic stabilization in polyaromatic cations, which is mainly attributed to the depletion of anti-aromaticity at the center ring. Further study showed an explicit correlation between the curvature of π-surface and the stability of adducts, aromatic behavior at center ring, as well as the spin distribution over polyaromatic moiety. By curving the π-surface, we have proposed several buckybowl radical adducts and confirmed their stability. These models provide an alternative strategy of developing polyaromatic spin carriers, which have a great potential in the manufacture of quantum bits. We believe our comprehensive theoretical study on versatile chemistry of buckybowl and related polyaromatic hydrocarbons can offer fundamental understanding and essential guidance for developing buckybowl-based electrode materials in the lithium-ion battery, organometallic building block, and spin electronic devices. Show less
