The unique sandwich K6Be2B6H6 cluster with a real borozene B6H6 core.

Theoretical evidence is reported for a boron-based K6Be2B6H6 sandwich cluster, showing a perfectly D 6h B6H6 ring, being capped by two tetrahedral K3Be ligands. Due to the comfortable charge transfer, the sandwich is viable in [K3Be]3+[B6H6]6-[BeK3]3+ ionic complex in nature. The [B6H6]6- core with 6π aromaticity vividly imitates the benzene (C6H6), occurring as a real borozene. In contrast, the tetrahedral [K3Be]3+ ligand is 2σ three-dimensional aromatic, acting as the simple superatom. Thus, this complex possesses a collectively three-fold 2σ/6π/2σ aromaticity. The interlaminar interaction is governed by the robust electrostatic attraction. The unique chemical bonding gives rise to interesting dynamic fluxionality.