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.