The domain of aromaticity spans a wide range of molecules, from polycyclic aromatic hydrocarbons, heterocycles to all-metal systems. Here, in silico we demonstrate the aromaticity in CBF, extending beyond the limit of conventional aromatic molecules. This molecule gains the magic number of six π-electrons through an unusual electronic contribution from exo-cyclic atoms. The stability of the molecule is established through density functional theory, ab initio calculations as well as molecular dynamics simulation.

Illustration of bond stretch isomerization of triangular D3h Be32− moieties via the linear D∞h intermediate through the Renner–Teller effect. The reactant, intermediate and products are connected schematically by the C2v transition states; moreover, a connection between the transition states and excited state linear intermediate is depicted.

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Aromaticity is an important concept in chemistry which extends over a wide range of molecular systems and imparts unique features to the molecules possessing it. In the present work, novel heteroatomic molecular systems are proposed which demonstrate non-conventional aromaticity where the molecules accomplish the aromatic sextet and hence stabilization through the conjugation of π-electrons from exo-cyclic substituents. A considerable σ-aromaticity is also observed which does not involve the exo-cyclic atoms. At first, the stability of these molecular systems is theoretically ascertained through various density functional theory and ab-initio calculations along with the energy decomposition analysis, T 1 diagnostic run, estimation of ring strain energy and highest occupied molecular orbital-lowest unoccupied molecular orbital gap which indicate towards the viability of these molecular systems. Then, a detailed study of aromaticity with the aid of different computational probes such as nucleus-independent chemical shift (NICS), dissected canonical molecular orbital-NICS analysis, multi-centre bond index (MCI), adaptive natural density partitioning and theoretical tools such as aromatic stabilization energy based on a fully ab-initio approach are performed which establish unique exo-cyclic aromaticity in these systems.