LAUSR

Multi-layer molecular rotors represent a class of unique combination of topology and bonding, featuring a barrier-free rotation of one layer with respect to other layers. This emerging fluxional behavior has been found in a few doped boron clusters. Herein, we strongly enrich this intriguing family followed by an effective design strategy, summarized as essential factors: i) considerable electrostatic interactions originated from a strong charge transfer between layers; ii) the absence of strong covalent bonds between layers; and iii) fully delocalized σ/π electrons from at least one layer. We found that planar hypercoordinate motifs consisting of monocyclic boron rings and metals with σ + π dual aromaticity can be regarded as one promising layer, which can support the suspended X2 (X = Zn, Cd, Hg) dimers. By detailed investigations of thermodynamic and kinetic stabilities of 60 species, eventually, MB7 X2 - and MB8 X2 (X = Zn, Cd; M = Be, Ru, Os; Be works only for Zn-based cases) clusters were verified to be the global-minimum two-layer molecular rotors. Especially, their electronic structure analyses vividly confirm the practicability of the electronic structure requirements mentioned above for designing multi-layer molecular rotors.