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 D7h La2B7- (1), D8h La2B8 (3), D9h La2B9- (7) can be extended to their actinide counterparts C2v Ac2B7- (1'), D8h Ac2B8 (3'), D9h Ac2B9- (7') with a Bn monocyclic ring (n = 7-9) sandwiched by two Ac dopants. Such M2Bn-/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'), C3v/C3 La4B18 (5)/Ac4B18 (5'), Oh Ac7B24+ (6'), Oh Ac7B24, Td Ac4B24 (8'), C1 La5B24+ (9)/Ac5B24+ (9'), and Td Ac4B29- (10') which are based on boron frameworks consisting of multiple conjoined Bn 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 Bn rings and metal doping centers, conferring three-dimensional aromaticity and extra stability to the systems. In particular, the perfect body-centered cubic Oh Ac7B24+ (6') and Oh 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.