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La@[La5&B30]0/−/2−: endohedral trihedral metallo-borospherenes with spherical aromaticity.
- Source :
- Physical Chemistry Chemical Physics (PCCP); 2/14/2022, Vol. 24 Issue 6, p3918-3923, 6p
- Publication Year :
- 2022
-
Abstract
- 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 D<subscript>8h</subscript> [La(η<superscript>8</superscript>-B<subscript>8</subscript>)La] and D<subscript>9h</subscript> [La(η<superscript>9</superscript>-B<subscript>9</subscript>)La]<superscript>−</superscript>. Based on extensive global minimum searches and first-principles theory calculations, we predict herein the possibility of perfect endohedral trihedral metallo-borospherene D<subscript>3h</subscript> La@[La<subscript>5</subscript>&B<subscript>30</subscript>] (1, <superscript>3</superscript>A′<subscript>1</subscript>) and its monoanion C<subscript>s</subscript> La@[La<subscript>5</subscript>&B<subscript>30</subscript>]<superscript>−</superscript> (2, <superscript>2</superscript>A′) and dianion D<subscript>3h</subscript> La@[La<subscript>5</subscript>&B<subscript>30</subscript>]<superscript>2−</superscript> (3, <superscript>1</superscript>A′<subscript>1</subscript>). These La-doped boron clusters are composed of three inverse sandwich La(η<superscript>8</superscript>-B<subscript>8</subscript>)La on the waist and two inverse sandwich La(η<superscript>9</superscript>-B<subscript>9</subscript>)La on the top and bottom which share one apex La atom at the center and six periphery B<subscript>2</subscript> units between neighboring η<superscript>8</superscript>-B<subscript>8</subscript> and η<superscript>9</superscript>-B<subscript>9</subscript> 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<subscript>5</subscript>&B<subscript>30</subscript>]<superscript>0/−/2−</superscript> (1/2/3) are spherically aromatic in nature. The one-dimensional nanowire La<subscript>4</subscript>B<subscript>21</subscript> (4, P31m) constructed from D<subscript>3h</subscript> La@[La<subscript>5</subscript>&B<subscript>30</subscript>] (1) along the C<subscript>3</subscript> axis of the system appears to be metallic. The IR and Raman spectra of La@[La<subscript>5</subscript>&B<subscript>30</subscript>] (1) and photoelectron spectroscopy of the slightly distorted C<subscript>s</subscript> La@[La<subscript>5</subscript>&B<subscript>30</subscript>]<superscript>−</superscript> (2) are theoretically simulated to facilitate their spectroscopic characterizations. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 14639076
- Volume :
- 24
- Issue :
- 6
- Database :
- Complementary Index
- Journal :
- Physical Chemistry Chemical Physics (PCCP)
- Publication Type :
- Academic Journal
- Accession number :
- 155141968
- Full Text :
- https://doi.org/10.1039/d1cp05644a