Planar Elongated B₁₂ Structure in M₃B₁₂ Clusters (M = Cu-Au)

Here, it is shown that the M₃B₁₂ (M = Cu-Au) clusters’ global minima consist of an elongated planar B₁₂ fragment connected by an in-plane linear M₃ fragment. This result is striking since this B₁₂ planar structure is not favored in the bare cluster, nor when one or two metals are added. The minimum energy structures were revealed by screening the potential energy surface using genetic algorithms and density functional theory calculations. Chemical bonding analysis shows that the strong electrostatic interactions with the metal compensate for the high energy spent in the M₃ and B₁₂ fragment distortion. Furthermore, metals participate in the delocalized π-bonds, which infers an aromatic character to these species.