Theoretical prediction of superatomic orbitals in spherical trihedral metallo-borospherenes Be3B12+1/+2

Abstract

Superatomic molecular orbitals (SAMOs) have attracted particular attention due to the efficient overlapping of electronic wave functions between adjacent molecules, a key factor for enhancing charge transfer in molecular materials. Inspired by the recently discovered spherical trihedral metallo-borospherenes D3h Ln3B18– (Ln = La, Tb), of which both the B18-framework and the three Ln atoms are integral parts of surface cages, here we conceive the smallest spherical trihedral metallo-borospherenes with B6 motifs to date, D3h Be3B12+1/+2, which possess two equivalent directly connected B6 triangles, without any linking units at the jointing vertices, forming three equivalent η6-B6 rings and each centered with a Be atom. Interestingly, the hypothesized cage-like structure is proved to be with the lowest energy for each composition, and possesses SAMOs characters, of which the electronic configurations are 1S21P61D101F62S21F82P61Gα11Gβ0 and 1S21P61D101F62S21F82P61G0, corresponding to the systems with one or two positive charges, respectively. Our finding of SAMOs in the frontier orbitals of spherical trihedral metallo-borospherene furnishes a potential molecular unit for charge transport using superatomic channels.