La@[La5&B30]0/-/2-: endohedral trihedral metallo-borospherenes with spherical aromaticity

It is well-known that transition-metal-doping induces dramatic changes in the structures and bonding of small boron dusters, as demonstrated by the newly observed perfect inverse sandwich D-8h [La(eta(8)-B-8)La] and D-9h[La(eta(9)-B-9)La](-). Based on extensive global minimum searches and first-principles theory calculations, we predict herein the possibility of perfect endohedral trihedral metao-borospherene D-3h center dot La@[La-5&B-30] (1, (3)A(1)') and its monoanion C-s La@[La-5&B-30](-) (2, (2)A') and dianion D-3h La@[La-5&B-30](2- )(3, (1)A(1)'). These La-doped boron dusters are composed of three inverse sandwich La(eta(8)-B-8)La on the waist and two inverse sandwich La(eta(9)-B-9)La on the top and bottom which share one apex La atom at the center and six periphery B-2 units between neighboring eta(8)-B-8 and eta(9)-B-9 rings, with three octocoordinate 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-5&B-30](0/-/2-) (1/2/3) are spherically aromatic in nature. The one-dimensional nanowire La4B21 (4, P31m) constructed from D-3h La@[La-5&B-30] (1) along the C3 axis of the system appears to be metallic. The IR and Raman spectra of La@[La-5&B-30] (1) and photoelectron spectroscopy of the slightly distorted C-s La@[La-5&B-30](-) (2) are theoretically simulated to facilitate their spectroscopic characterizations.

Automated summary

Transition metal doping induces significant changes in the structures and bonding of small boron clusters, and new structures and properties of lanthanum-doped boron clusters are predicted.