La@[La 5 &B 30 ] 0/-/2- : endohedral trihedral metallo-borospherenes with spherical aromaticity

• Published in: Physical chemistry chemical physics : PCCP 2022-02, Vol.24 (6), p.3918-3923
• Main Authors: Ao, Mei-Zhen, Lu, Xiao-Qin, Mu, Yue-Wen, Zan, Wen-Yan, Li, Si-Dian
• Format: Article
• Language: English
• Subjects: Anions; Aromaticity; Boron; Clusters; First principles; Metallography; Nanowires; Photoelectrons; Raman spectra; Shielding; Spectrum analysis; Transition metals
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d1cp05644a

It is well-known that transition-metal-doping induces dramatic changes in the structures and bonding of small boron clusters, as demonstrated by the newly observed perfect inverse sandwich [La(η -B )La] and [La(η -B )La] . Based on extensive global minimum searches and first-principles theory calculations, we predict herein the possibility of perfect endohedral trihedral metallo-borospherene La@[La &B ] (1, A' ) and its monoanion La@[La &B ] (2, A') and dianion La@[La &B ] (3, A' ). These La-doped boron clusters are composed of three inverse sandwich La(η -B )La on the waist and two inverse sandwich La(η -B )La on the top and bottom which share one apex La atom at the center and six periphery B units between neighboring η -B and η -B rings, with three octo-coordinate La atoms and two nona-coordinate La atoms as integrated parts of the cage surface. Detailed adaptive natural density partitioning (AdNDP) and iso-chemical shielding surface (ICSS) analyses indicate that La@[La &B ] (1/2/3) are spherically aromatic in nature. The one-dimensional nanowire La B (4, 31 ) constructed from La@[La &B ] (1) along the axis of the system appears to be metallic. The IR and Raman spectra of La@[La &B ] (1) and photoelectron spectroscopy of the slightly distorted La@[La &B ] (2) are theoretically simulated to facilitate their spectroscopic characterizations.