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

Extensive global minimum searches augmented with first-principles theory calculations performed in this work indicate that the experimentally observed perfect inverse sandwich lanthanide boride complexes D_7h La₂B₇^- (1), D_8h La₂B₈ (3), D_9h La₂B₉^- (7) can be extended to their actinide counterparts C_2v Ac₂B₇^- (1'), D_8h Ac₂B₈ (3'), D_9h Ac₂B₉^- (7') with a B_n monocyclic ring (n = 7-9) sandwiched by two Ac dopants. Such M₂B_n^-/0 inverse sandwiches (1/1', 3/3', 7/7') can be used as building blocks to generate the ground-state C₂ La₄B₁₃^- (2)/Ac₄B₁₃^- (2'), D₂ La₄B₁₅^- (4)/Ac₄B₁₅^- (4'), C_3v/C₃ La₄B₁₈ (5)/Ac₄B₁₈ (5'), O_h Ac₇B₂₄⁺ (6'), O_h Ac₇B₂₄, T_d Ac₄B₂₄ (8'), C₁ La₅B₂₄⁺ (9)/Ac₅B₂₄⁺ (9'), and T_d Ac₄B₂₉^- (10') which are based on boron frameworks consisting of multiple conjoined B_n rings (n = 7-9). Detailed bonding analyses show that effective (d-p)σ, (d-p)π and (d-p)δ coordination bonds are formed between the B_n rings and metal doping centers, conferring three-dimensional aromaticity and extra stability to the systems. In particular, the perfect body-centered cubic O_h Ac₇B₂₄⁺ (6') and O_h Ac₇B₂₄ with six conjoined B₈ rings can be extended in x, y, and z dimensions to form one-dimensional Ac₁₀B₃₂ (11'), two-dimensional Ac₃B₁₀ (12'), and three-dimensional AcB₆ (13') nanomaterials, presenting a B₈-based bottom-up approach from metal boride nanoclusters to their low-dimensional nanomaterials.