Li₂B₁₂ and Li₃B₁₂: Prediction of the Smallest Tubular and Cage‐like Boron Structures

Abstract

An intriguing structural transition from the quasi-planar form of B cluster upon the interaction with lithium atoms is reported. High-level computations show that the lowest energy structures of LiB , Li B , and Li B have quasi-planar (C ), tubular (D ), and cage-like (C ) geometries, respectively. The energetic cost of distorting the B quasi-planar fragment is overcompensated by an enhanced electrostatic interaction between the Li cations and the tubular or cage-like B fragments, which is the main reason of such drastic structural changes, resulting in the smallest tubular (Li B ) and cage-like (Li B ) boron structures reported to date.

Probing the structure and electronic properties of beryllium doped boron clusters: A planar BeB16− cluster motif for metallo-borophene

“…Recently, systematic investigations of pure boron clusters in term of the anisotropy and polymorphism have brought forth new significant findings leading to the design of new borides. A selection of characteristic architectures of pure boron clusters includes: tank tread 34 , wankel motor 35–39 , wheel-like 40 , boron nanotubes 41 , B 12 icosahedra 42 , buckyballs 43 , fullerene 44 , B 36 with hexagonal holes (HHs) 45 , naphthalene 46 , borospherene 47 and more. Co and Rh doped B 12 − clusters featured half-sandwich structure has been reported by Wang and co-workers 48 .…”

Structure evolution of chromium-doped boron clusters: toward the formation of endohedral boron cages

“…[26][27][28] The structural diversity of B clusters can be further enriched through metal doping. Metal-centered monocyclic B rings can be formed by transition metal doping of small B 8-10 anionic clusters 29 37 Metal doping has been proven to be an effective avenue to achieve intriguing structure motifs in B clusters. Given the large number of possible combinations between metal atoms and the number of B atoms yet to be investigated, it not unreasonable to expect more fascinating phenomena in this group of chemical species.…”

Triple‐ring tubular MB36 (M = Mg, Ca, Sr, Ba) with threefold aromaticity

“…A large number of studies have shown that metal modification can effectively compensate for the electron deficiency of boron and change the structures and properties of boron clusters [16‐33]. Joint photoelectron spectroscopy (PES) and first‐principles theory (FPT) investigations have shown that M©B n − (M = Co, Rh, Ir, Ru, Ta, Nb, n = 8–10) possess two dimensional (2D) wheels [16‐18].…”

“…Not only the type of the metals, the number of them also have significant influence on the structures of boron clusters [29‐33]. Two low‐lying isomers of binary Be 6 B 11 − : the coaxial triple‐layered cluster with structural fluxionality and helical cluster with multifold aromaticity, are anticipated to be co‐existence in the gas‐phase experiments [29].…”

“…Except the alkaline‐earth metals, the structural effects of alkali‐metals on the B 12 skeleton were also explored systematacially [30]. The enhanced electrostatic interaction between Li + and boron skeleton results in highly stable Li n B 12 ( n = 1–3) clusters which are in quasi‐planar, tubular, and cage‐like structures, respectively [31]. Doping B 24 with two lithium atoms results in the three‐ring tubular Li 2 B 24 [32].…”