Predicting lanthanide boride inverse sandwich tubular molecular rotors with the smallest core–shell structure

Abstract

Lanthanide–boron binary clusters possess interesting structures and bonding which may provide insights into designing new boride nanomaterials. Inspired by the recently discovered mono-decker inverse sandwich D_9h La₂B₉⁻ (¹A′₁) (1) and based on the extensive first-principles theory calculations, we predict herein the possible existence of a series of bi-decker inverse sandwich di-lanthanide boron complexes including D_9d La₂[B₁₈] (³A_1g) (2), D_9d La₂[B₁₈]²⁻ (¹A_1g) (3), and C_2h La₂[B₂@B₁₈] (¹A_g) (4) which all contain a tubular B_n ligand (n = 18, 20) sandwiched by two La atoms at the two ends. In these novel clusters, La₂[B₂@B₁₈] (4) as a tubular molecular rotor with the smallest core–shell structure reported to date in boron-based nanoclusters possesses a B₂-bar rotating constantly and almost freely inside the B₁₈ tube around it at room temperature. Detailed bonding analyses indicate that these complexes are stablized by effective (d–p)σ, (d–p)π, and (d–p)δ coordination interactions between the La centers and B_n bi-decker ligand. Six multi-center fluxional σ-bonds between the B₂-core and B₁₈ tube in La₂[B₂@B₁₈] (4) are found to be responsible for its unique fluxional behaviors. The IR and Raman spectra of the concerned species are simulated to facilitate their experimental characterization.