Antiaromaticity-aromaticity transition of cyclo[16]carbon upon metal encapsulation

In contrast to aromatic compounds with particular stability, antiaromatic compounds are usually less stable due to their high reactivity and unfavorable formation energies. Cyclo[16]carbon (C₁₆) is a carbon ring molecule with a dual antiaromatic character. In this study, we demonstrate that C₁₆ can be transformed into highly aromatic molecules upon metal encapsulation. The geometrical characteristics, electronic properties and thermodynamic stability of MC₁₆ compounds (M = Ca, Sc, Ti, V, Ce, U) are fully investigated from a theoretical perspective. Based on natural population analysis, atom-in-molecules theory and localized molecular orbital analysis, the nature of the metal-carbon interaction in the MC₁₆ compounds is investigated. It has been proved that the bonding between Ca and C₁₆ corresponds to a typical ionic interaction, while other metal atoms form polar covalent bonds with C₁₆. By analyzing the frontier molecular orbitals and magnetic response of MC₁₆, we have found that all the encapsulated metal atoms donate two electrons to the in-plane π orbitals via either electron transfer or orbital hybridization, which makes the in-plane π orbitals completely satisfy the 4n + 2 (n = 4) Hückel aromaticity rule. The U atom formally transfers four electrons to the carbon ring in total, two to the in-plane π orbitals and two to the out-of-plane π orbitals, which results in the remarkable dual aromaticity feature of UC₁₆. The transformation of aromaticity can be utilized to develop new strategies for the synthesis of novel carbon ring molecules.