From inverse sandwich Ta₂B₇ ⁺ and Ta₂B₈ to spherical trihedral Ta₃B₁₂ ^-: prediction of the smallest metallo-borospherene.

ABSTRACT: Transition-metal-doped boron nanoclusters exhibit interesting structures and bonding. Inspired by the experimentally discovered inverse sandwich D _6h Ta₂B₆ and spherical trihedral D _3h La₃B₁₈ ^- and based on extensive first-principles theory calculations, we predict herein the structural transition from perfect di-metal-doped inverse sandwich D _7h Ta₂B₇ ⁺ (1) and D _8h Ta₂B₈ (2) to tri-metal-doped spherical trihedral D _3h Ta₃B₁₂ ^- (3). As the smallest metallo-borospherene reported to date, Ta₃B₁₂ ^- (3) contains three octa-coordinate Ta atoms as integral parts of the cage surface coordinated in three equivalent η⁸-B₈ rings which share two eclipsed equilateral B₃ triangles on the top and bottom interconnected by three B₂ units on the waist. Detailed orbital and bonding analyses indicate that both Ta₂B₇ ⁺ (1) and Ta₂B₈ (2) possess σ + π dual aromaticity, while Ta₃B₁₂ ^- (3) is σ + π + δ triply aromatic in nature. The IR, Raman, and UV-vis or photoelectron spectra of the concerned species are computationally simulated to facilitate their future spectroscopic characterizations.

SUBMITTER: Zhang Y 

PROVIDER: S-EPMC9055930 | biostudies-literature | 2020 Aug

REPOSITORIES: biostudies-literature