Starting a subnanoscale tank tread: dynamic fluxionality of boron-based B10Ca alloy cluster

Abstract

Alloying an elongated B₁₀ cluster with Ca is shown to give rise to a dynamically fluxional B₁₀Ca cluster, the latter behaving like a tank tread at the subnanoscale. Computer global search identifies the B₁₀Ca C₂ (¹A) global-minimum structure, which is chiral in nature and retains the quasi-planar moiety of bare B₁₀ cluster with Ca capped at one side, forming a half-sandwich. The rotation barrier of B₁₀Ca cluster is reduced with respect to B₁₀ by one order of magnitude, down to 1 kcal mol⁻¹ at the PBE0/6-311+G* level, which demonstrates structural fluxionality at 600 K and beyond via molecular dynamics simulations. Structurewise, the Ca alloying in B₁₀Ca cluster generates rhombic defect holes, preactivating the species and making it flexible against deformation. Chemical bonding analyses indicate that the B₁₀Ca cluster is a charge-transfer [B₁₀]²⁻[Ca]²⁺ complex, being doubly π/σ aromatic with the 6π and 10σ electron-counting. Such a pattern offers ideal π/σ delocalization and facilitates fluxionality. In contrast, bare B₁₀ cluster has conflicting aromaticity with 6π and 8σ electrons, which is nonfluxional with a barrier of 12 kcal mol⁻¹. Double π/σ aromaticity versus conflicting aromaticity is a key mechanism that distinguishes between fluxional B₁₀Ca and nonfluxional B₁₀ clusters, offering a compelling example that the concept of aromaticity (and double aromaticity) can be exploited to design dynamically fluxional nanosystems.