Heptacoordinate transition-metal-decorated metallo-borospherenes and multiple-helix metallo-boronanotubes

Abstract

The recent discovery of lanthanide-metal-decorated metallo-borospherenes LM₃B₁₈⁻ (LM = La, Tb) marks the onset of a new class of boron-metal binary nanomaterials. Using the experimentally observed or theoretically predicted borospherenes as ligands and based on extensive first-principles theory calculations, we predict herein a series of novel chiral metallo-borospherenes C₂ Ni₆ ∈ B₃₉⁻ (1), C₁ Ni₆ ∈ B₄₁⁺ (3), C₂ Ni₆ ∈ B₄₂²⁺ (4), C₂ Ni₆ ∈ B₄₂ (5), and C₂ Ni₈ ∈ B₅₆ (6) as the global minima of the systems decorated with quasi-planar heptacoordinate Ni (phNi) centers in η⁷-B₇ heptagons on the cage surfaces, which are found to be obviously better favoured in coordination energies than hexacoordinate Ni centers in previously reported D_2d Ni₆ ∈ B₄₀ (2). Detailed bonding analyses indicate that these phNi-decorated metallo-borospherenes follow the σ + π double delocalization bonding pattern, with two effective (d–p)σ coordination bonds formed between each phNi and its η⁷-B₇ ligand, rendering spherical aromaticity and extra stability to the systems. The structural motif in elongated axially chiral Ni₆ ∈ B₄₂²⁺ (4), Ni₆ ∈ B₄₂ (5), and Ni₈ ∈ B₅₆ (6) can be extended to form the metallic phNi-decorated boron double chain (BDC) double-helix Ni₄ ∈ B₂₈ (2, 0) (Pm2) (8), triple-helix Ni₆ ∈ B₄₂ (3, 0) (Pm1) (9), and quadruple-helix Ni₈ ∈ B₅₆ (4, 0) (P4mm) (10) metallo-boronanotubes, which can be viewed as quasi-multiple-helix DNAs composed of interconnected BDCs decorated with phNi centers in η⁷-B₇ heptagons on the tube surfaces in the atomic ratio of Ni : B = 1 : 7.