Coaxial Triple‐Layered versus Helical Be₆B₁₁⁻ Clusters: Dual Structural Fluxionality and Multifold Aromaticity

Abstract

Two low-lying structures are unveiled for the Be₆ B₁₁^- nanocluster system that are virtually isoenergetic. The first, triple-layered cluster has a peripheral B₁₁ ring as central layer, being sandwiched by two Be₃ rings in a coaxial fashion, albeit with no discernible interlayer Be-Be bonding. The B₁₁ ring revolves like a flexible chain even at room temperature, gliding freely around the Be₆ prism. At elevated temperatures (1000 K), the Be₆ core itself also rotates; that is, two Be₃ rings undergo relative rotation or twisting with respect to each other. Bonding analyses suggest four-fold (π and σ) aromaticity, offering a dilute and fluxional electron cloud that lubricates the dynamics. The second, helix-type cluster contains a B₁₁ helical skeleton encompassing a distorted Be₆ prism. It is chiral and is the first nanosystem with a boron helix. Molecular dynamics also shows that at high temperature the helix cluster readily converts into the triple-layered one.