Boron-based Pd3B26 alloy cluster as a nanoscale antifriction bearing system: tubular core–shell structure, double π/σ aromaticity, and dynamic structural fluxionality

Abstract

Boron-based nanoclusters show unique geometric structures, nonclassical chemical bonding, and dynamic structural fluxionality. We report here on the theoretical prediction of a binary Pd₃B₂₆ cluster, which is composed of a triangular Pd₃ core and a tubular double-ring B₂₆ unit in a coaxial fashion, as identified through global structural searches and electronic structure calculations. Molecular dynamics simulations indicate that in the core–shell alloy cluster, the B₂₆ double-ring unit can rotate freely around its Pd₃ core at room temperature and beyond. The intramolecular rotation is virtually barrier free, thus giving rise to an antifriction bearing system (or ball bearing) at the nanoscale. The dimension of the dynamic system is only 0.66 nm. Chemical bonding analysis reveals that Pd₃B₂₆ cluster possesses double 14π/14σ aromaticity, following the (4n + 2) Hückel rule. Among 54 pairs of valence electrons in the cluster, the overwhelming majority are spatially isolated from each other and situated on either the B₂₆ tube or the Pd₃ core. Only one pair of electrons are primarily responsible for chemical bonding between the tube and the core, which greatly weaken the bonding within the Pd₃ core and offers structural flexibility. This is a key mechanism that effectively diminishes the intramolecular rotation barrier and facilitates dynamic structural fluxionality of the system. The current work enriches the field of nanorotors and nanomachines.