Perfect cubic La-doped boron clusters La(6)&[La@B(24)](+/0) as the embryos of low-dimensional lanthanide boride nanomaterials

La-doped boron nanoclusters have received considerable attention due to their unique structures and bonding. Inspired by recent experimental observations of the inverse sandwich D(8h) La(2)B(8) (1) and triple-decker C(2v) La(3)B(14)(−) (2) and based on extensive global searches and first-principles theory investigations, we present herein the possibility of the perfect cubic La-doped boron clusters O(h) La(6)&[La@B(24)](+) (3, (1)A(1g)) and O(h) La(6)&[La@B(24)] (4, (2)A(2g)) which appear to be the embryos of the metallic one-dimensional La(10)B(32) (5) nanowire, two-dimensional La(3)B(10) (6) nanosheet, and three-dimensional LaB(6) (7) nanocrystal, facilitating a bottom-up approach to build cubic lanthanide boride nanostructures from gas-phase clusters. Detailed molecular orbital and bonding analyses indicate that effective (d–p)σ, (d–p)π and (d–p)δ covalent coordination interactions exist in La(6)&[La@B(24)](+/0) (3/4) clusters, while the 1D La(10)B(32) (5), 2D La(3)B(10) (6), and 3D LaB(6) (7) crystals exhibit mainly electrostatic interactions between the trivalent La centers and cubic B(24) frameworks, with weak but discernible coordination contributions from La (5d) ← B (2p) back-donations. The IR and Raman spectra of La(6)&[La@B(24)](+/0) (3/4) and band structures of La(10)B(32) (5) and La(3)B(10) (6) are computationally simulated to facilitate their future characterizations.