LAUSR

Two new structural motifs of the B24 clusters are constructed by use of the leapfrog transformation. The resulting leapfrog B24 has either a bowl shape with a square vacancy or a quasi‐planar 2D close‐packed triangular boron sheet. The neutral and ionic forms of the latter are found to be more stable than their homologous leapfrog bowl clusters, with the exception of the dicationic B24+2. While the leapfrog isomer is less stable than the tubular double ring in the neutral state, it becomes competitive in some ionic states. The nucleus independent chemical shift, electron localization function, ring current maps and the electronic structure of leapfrog B24 clusters reveal them to behave as aromatics.