Axially Chiral Cage-Like B 38 + and B 38 2+ : New Aromatic Members of the Borospherene Family
- PDF / 2,024,366 Bytes
- 7 Pages / 595.276 x 790.866 pts Page_size
- 12 Downloads / 136 Views
(0123456789().,-volV)(0123456789().,-volV)
ORIGINAL PAPER
Axially Chiral Cage-Like B38+ and B382+: New Aromatic Members of the Borospherene Family Hui Liu1 • Yue-Wen Mu1 • Si-Dian Li1 Received: 2 March 2020 / Accepted: 9 November 2020 Ó Springer Science+Business Media, LLC, part of Springer Nature 2020
Abstract The successive discoveries of the cage-like D2d B40-/0 and C3/C2 B39- mark the onset of borospherene chemistry. Based on extensive global minimum searches and first-principles theory calculations, we predict herein the possible existence of the axially chiral cage-like C2 B38? (1/10 ) and C2 B382? (3/30 ) which are novel aromatic members of the borospherene family featuring a B21 boron triple-chain on the waist and four B6 hexagonal holes on the cage surface. Detailed bonding analyses show that the B38? (1) and B382? (3) possess 12 and 11 delocalized p bonds over a r-skeleton, respectively, following the universal bonding pattern of r ? p double delocalization of the borospherene family. Extensive molecular dynamics simulations indicate that both B38? (1) and B382? (3) are dynamically stable at 700 K. The IR, Raman, and UV–vis spectra of these cluster cations are computationally simulated to facilitate their future spectral characterizations. Keywords First-principles theory Boron clusters Borospherenes Structures Bonding
Introduction As prototypical electron-deficient element in the periodical table, boron exhibits strong propensity to form delocalized multicenter-two-electron (mc-2e) bonds in both bulk allotropes and polyhedral molecules [1–3]. Over the past two decades, anionic boron clusters Bn- (n = 3–38,41,42) have been systematically confirmed to possess planar or quasiplanar (2D) global minimum (GM) structures via joint photoelectron spectroscopy (PES) and extensive firstprinciples theory investigations [4–16]. 2D Bn- clusters featuring both delocalized mc-2e r and p bonds are composed of B3 triangular networks with certain numbers of polygonal holes. After the discovery of the perfect quasi-
Electronic supplementary material The online version of this article (https://doi.org/10.1007/s10876-020-01943-z) contains supplementary material, which is available to authorized users. & Yue-Wen Mu [email protected] & Si-Dian Li [email protected] 1
Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006, Shanxi, People’s Republic of China
planar B36-/0 cluster with a hexagonal hole at the center in 2014, [14] more 2D boron clusters with a double hexagonal vacancy (DHV) were observed, including B35-, B37-, B38-, [13, 15] and the more recently reported B41- and B42- clusters [16], providing indirect evidence for the existence of 2D all-boron sheets dubbed borophenes with various hexagonal vacancy densities. [14, 17, 18] Supported polymorphous borophenes on various metal substrates were prepared using molecular beam epitaxy (MBE) method [19–22]. A major breakthrough in the studies of boron clusters occurred in 2014 when the first all-boron fullerenes D2d B40-/0, du
Data Loading...
