Donor–acceptor duality of the transition-metal-like B2 core in core–shell-like metallo-borospherenes La3&[B2@B17]− and La3&[B2@B18]−

Abstract

Transition-metal doping induces dramatic structural changes and leads to earlier planar → tubular → spherical → core–shell-like structural transitions in boron clusters. Inspired by the newly discovered spherical trihedral metallo-borospherene D_3h La₃&B₁₈⁻ (1) (Chen, et al., Nat. Commun., 2020, 11, 2766) and based on extensive first-principles theory calculations, we predict herein the first and smallest core–shell-like metallo-borospherenes C_2v La₃&[B₂@B₁₇]⁻ (2) and D_3h La₃&[B₂@B₁₈]⁻ (3) which contain a transition-metal-like B₂ core at the cage center with unique donor–acceptor duality in La₃&B_n⁻ spherical trihedral shells (n = 17, 18). Detailed energy decomposition and bonding analyses indicate that the B₂ core in these novel complexes serves as a π-donor in the equatorial direction mainly to coordinate three La atoms on the waist and a π/σ-acceptor in the axial direction mainly coordinated by two B₆ triangles on the top and bottom. These highly stable core–shell complexes appear to be spherically aromatic in nature in bonding patterns. The IR, Raman, and photoelectron spectra of 2 and 3 are computationally simulated to facilitate their spectroscopic characterizations.