A bottom-up approach from medium-sized bilayer boron nanoclusters to bilayer borophene nanomaterials

Abstract

Inspired by the experimentally observed bilayer B₄₈^−/0 and theoretically predicted bilayer B₅₀–B₇₂ and based on extensive density functional theory calculations, we report herein a series of novel medium-sized bilayer boron nanoclusters C₁ B₈₄ (I), C_2v B₈₆ (II), C₁ B₈₈ (III), C₁ B₉₀ (IV), C₁ B₉₂ (V), C₁ B₉₄ (VI), C_2v B₉₆ (VII), and C₁ B₉₈ (VIII) which are the most stable isomers of the systems reported to date effectively stabilized by optimum numbers of interlayer B–B σ bonds between the inward-buckled atoms on top and bottom layers. Detailed bonding analyses indicate that these bilayer species follow the universal bonding pattern of σ + π double delocalization, rendering three-dimensional aromaticity in the systems. More interestingly, the AA-stacked bilayer structural motif in B₉₆ (VII) with a B₇₂ bilayer hexagonal prism at the center can be extended to form bilayer C₂ B₁₂₈ (IX), D_2h B₂₁₄ (X), C_2v B₂₆₀ (XI), D_2h B₃₇₂ (XII), and D₂ B₈₂₈ (XIII) which contain one or multiple conjoined B₇₂ bilayer hexagonal prisms sharing interwoven zig-zag boron triple chains between them. Such bilayer species or their close-lying AB isomers can be viewed as embryos of the newly reported most stable freestanding BL-α⁺ bilayer borophenes and quasi-freestanding bilayer borophenes on Ag(111) which are composed of interwoven zig-zag boron triple chains shared by conjoined BL B₇₂ hexagonal prisms, presenting a bottom-up approach from medium-sized bilayer boron nanoclusters to two-dimensional bilayer borophene nanomaterials.