Bilayer B₅₄, B₆₀, and B₆₂ Clusters in a Universal Structural Pattern

Abstract

Boron nanoclusters and few‐layer borophenes have received considerable attention in recent years due to their unique structural and bonding patterns. Based on extensive global searches and density‐functional theory calculations, we present herein the possibility of a new series of bilayer medium‐sized boron clusters including C2 B54 (I), C2h B60 (II), and C1 B62 (III) in a universal structural pattern, with one, two, and three B6 hexagonal windows on the waist around a B38 bilayer hexagonal prism at the center, respectively. Detailed orbital and bonding analyses indicate that these three‐dimensional aromatic bilayer clusters follow the σ + π double delocalization bonding pattern, with three or four effective interlayer B–B σ‐bonds formed to further stabilize the system. The IR, Raman, and UV/Vis spectra of the bilayer species are theoretically simulated to facilitate their future spectral characterizations.

Perfect Spherical Tetrahedral Metallo-Borospherene Ta4B18 as a Superatom Following the 18-Electron Rule

“… 16 Extensive GM searches and DFT calculations showed that B 46 is the smallest core–shell boron cluster with a B 4 core at the center (B 4 @B 42 ), while B 48 , B 54 , B 60 , and B 62 are the first bilayer boron clusters predicted to date. 17 , 18 Encouragingly, bilayer B 48 –/0 has been very recently confirmed in gas-phase PES measurements, revealing a new structural domain in boron nanoclusters and nanomaterials. 19 …”

“… 63 Chemical bonding was analyzed using the adaptive natural density partitioning (AdNDP) method, 43 , 43 which has been successfully applied to various organic and inorganic species. 2 − 10 , 18 , 19 Molecular dynamics (MD) simulations were carried out on T d Ta 4 B 18 for 30 ps using a CP2K software suite. 64 The iso-surface maps of various orbitals and the iso-chemical shielding surfaces (ICSSs) were realized using the visual molecular dynamics (VMD) software.…”

Cage-Like La4B24 and Core-Shell La4B290/+/-: Perfect Spherically Aromatic Tetrahedral Metallo-Borospherenes

“…Joint ion-mobility measurements and density functional theory (DFT) investigations indicated that boron cluster monocations (B n + ) possess double-ring tubular geometries in the size range between n = 16-25 [12]. Extensive GM searches showed that complicated structural competitions exist in medium-sized B n clusters, with B 46 being the smallest core-shell boron cluster (B 4 @B 42 ) and B 48 , B 54 , B 60 , and B 62 being the rst bilayer boron clusters predicted to date [13,14].…”

Donor–acceptor duality of the transition-metal-like B2 core in core–shell-like metallo-borospherenes La3&[B2@B17]− and La3&[B2@B18]−

“…[13][14][15][16] More complicated structural competitions exist in mediumsized boron clusters, with B 46 being theoretically predicted to be the smallest core-shell-like boron cluster reported to date, while B 48 , B 54 , B 60 , and B 62 are proposed to possess bilayer structures. 17,18 Joint ion-mobility experiments and density functional theory (DFT) investigations, on the other hand, indicated that bare B n + boron cluster monocations possess double-ring tubular structures in the size range between n ¼ 16-25. 19 Transition-metal-doping induces dramatic structural changes and leads to earlier planar / tubular / spherical / core-shell-like structural transitions in boron clusters.…”