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

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 D8h [La(η8‒B8)La] and D9h...

Lanthanide/actinide boride nanoclusters and nanomaterials based on boron frameworks consisting of conjoined Bnrings (n= 7–9)

“…Obviously, the space inside the complexes or within about 1.0 Å above the metal atoms in vertical direction belong to chemical shielding regions with negative NICS-ZZ values (highlighted in yellow), while the chemical de-shielding areas with positive NICS values (highlighted in green) are located outside the B n ligands in horizontal direction. The ICSSs of these complexes appear to be similar to that of the prototypical aromatic benzene C 6 H 6 33.…”

“…The ICSSs of these complexes appear to be similar to that of the prototypical aromatic benzene C 6 H 6 . 33…”

“…29 Based on extensive global minimum (GM) searches and first-principles theory calculations, our group recently proposed a series of novel lanthanide boride nanoclusters including the smallest double-ring tubular molecular rotor C 2h La 2 [B 2 @B 18 ] with a B 2 dumb-bell inside, 30 perfect endohedral cubic O h La 7 B 24 + ( 6 ) and O h La 7 B 24 with six conjoined inverse La 2 B 8 sandwiches sharing a La atom at the center, perfect tetrahedral metallo-borospherene T d La 4 B 24 ( 8 ) with four nona-coordinate La atoms on the cage surface, perfect tetrahedral core–shell metallo-borospherene T d La 4 B 29 0/+/− ( 10 ) (B@B 4 @La 4 B 24 ) with a tetrahedral BB 4 unit at the center, and endohedral trihedral metallo-borospherenes D 3h La@[La 5 &B 30 ] 0/2− with spherical aromaticity. 31–33 However, tetra-La-doped boride complexes La 4 B n −/0 ( n = 13–18) with conjoined B 7 , B 8 , and B 9 rings as ligands still remain unknown in both experiments and theory, and more importantly, the chemistry and materials science of the corresponding actinide boride nanoclusters and their low-dimensional nanomaterials have not been explored to date in either experiments or theory possibly due to the radioactivity of actinide. Modern quantum chemistry provides powerful means to fulfil the gaps in such situations.…”

“…(8) with four nona-coordinate La atoms on the cage surface, perfect tetrahedral core-shell metallo-borospherene T d La 4 B 29 0/+/À (10) (B@B 4 @La 4 B 24 ) with a tetrahedral BB 4 unit at the center, and endohedral trihedral metallo-borospherenes D 3h La@[La 5 &B 30 ] 0/2À with spherical aromaticity [31][32][33]. However, tetra-La-doped boride complexes La 4 B n À/0 (n = 13-18) with conjoined B 7 , B 8 , and B 9 rings as ligands still remain unknown in both experiments and theory, and more importantly, the chemistry and materials science of the corresponding actinide boride nanoclusters and their low-dimensional nanomaterials have not been explored to date in either experiments or…”

Large B7 Triangles in Hollow Spherical Trihedral Metallo-borospherenes and Their Endohedral Complexes of B20TMn (TM = Sc, Y; n = 3, 4): a Theoretical Characterization

“…The perfect cubic O h [B 24 @La]&La 6 +/– can be derived from two C 2 v B 14 La 3 – clusters, only possessing B 3 triangles . Endohedral trihedral metallo-borospherenes [B 30 &La 5 ]@La 0/–/2– reported earlier this year is an exception, with a larger B 30 skeleton on its cage surface, but has three tetragonal defects . It is natural to ask whether there exists a spherical trihedral metallo-borospherene with the stability favoring over other low-lying isomers, the B triangles of the cage surface larger than the known B 6 triangle, and no defects.…”