Understanding the Central Location of a Hexagonal Hole in a B<sub>36</sub> Cluster

Liu, Lei; Osorio, Edison; Heine, Thomas

doi:10.1002/asia.201601106

Cited by 8 publications

(23 citation statements)

References 37 publications

(86 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[35] The role of the hexagonal vacancy in the stability of B 36 has been further analyzed recently. [62] The hexagonal vacancy in the global minima of B 33 and B 34 implies that B 35 is the smallest cluster to possess a double-hexagonal vacancy. [40] It is interesting to see the evolution of the double-hexagonal vacancy among the low-lying isomers in B 33 and B 34 -.…”

Section: Structural Evolution In Mid-sized Boron Clustersmentioning

confidence: 99%

B₃₃^– and B₃₄^–: Aromatic Planar Boron Clusters with a Hexagonal Vacancy

Chen

Zhao

et al. 2017

Eur J Inorg Chem

View full text Add to dashboard Cite

Systematic experimental and theoretical studies have shown that anionic boron clusters (B n -) possess planar or quasi-planar (2D) structures in a wide range of cluster size. The 2D structures consist of B 3 triangles often decorated with tetragonal and pentagonal defects. As n increases, hexagonal vacancies appear to be a key structural feature, which underlies the stability of borophenes. The correlation of the defects with cluster size is important to understand the stability and structural evolution of boron clusters. Here we report an investigation of the structures and chemical bonding of B 33 -and B 34 -using photoelectron spectroscopy (PES) and density functional

show abstract

Section: Structural Evolution In Mid-sized Boron Clustersmentioning

confidence: 99%

B₃₃^– and B₃₄^–: Aromatic Planar Boron Clusters with a Hexagonal Vacancy

Chen

Zhao

et al. 2017

Eur J Inorg Chem

View full text Add to dashboard Cite

show abstract

“…More interestingly, several totally delocalized 36-center 2-electron (36c-2e) π-bonds were found from the chemical bonding analysis. A recent study reveals that delocalized 36c-2e π-bonds as well as three delocalized 12-center 2-electron (12c-2e) π-bonds around the central hexagonal hole are the reasons for the high stability of this structure [26]. The largest boron cluster that has been confirmed to be planar so far is B 40 − .…”

Section: Planar Boron Clustersmentioning

confidence: 98%

Geometries and Electronic Structures of Boron Clusters: Planar Structures and All-boron Fullerenes

Liu¹

2016

J Apl Theol

Self Cite

View full text Add to dashboard Cite

[5]. Thus, they attract the interests of interdisciplinary researchers. A primary task in the research of boron clusters is to find the most stable structures of clusters containing given numbers and types of atoms. In this mini-review, we summarize the geometries and electronic structures of two commonly studied boron clusters, planar boron clusters and all-boron fullerenes. Planar Boron ClustersIn the solid state, boron compounds often adopt threedimensional (3D) structures [6][7][8][9][10]. One heavily studied type is boranes of general form B n H n . Most of the boranes are shown to be cage-like, referred as deltahedra [11]. The representative example is B 12 H 12 2− , which was first theoretically investigated by Longuet-Higgins and Roberts using molecular orbital theory [12]. They concluded that the B 12 H 12 structure could be stable only as a di-anion, B 12 H 12 2− , having 13 skeletal bonding orbitals and 12 outward pointing external orbitals. This hypothesis was confirmed later by experimental data, and the structure of B 12 H 12 2− anion was shown to be icosahedral [13]. Unlike 3D cage structures, which are the dominant configurations of boron compounds in the solid state, the pure small boron clusters (n ≤ 40) are found to be two-dimensional (2D) planar or quasi-planar in the gas phase, and the chemical bonding analysis suggests that this planarity is a consequence of π bonding in the cluster forms [9,10]. The simplest pure boron cluster is the diatomic B 2 , which serves as the first example of unusual chemical bonding in the boron species. On the basis of Hartree-Fock and UMP4 (unrestricted fourth order Møller-Plesset perturbation theory) calculations [14], the next pure boron cluster, B 3 , is shown to exist in cationic or anionic forms with a triangular structure of D 3h symmetry.In 2004, Zubarev et al concluded that pure boron clusters containing up to 15 atoms retain planar or quasi-planar conformation [15]. However, there still remains a strong interest to determine the critical size at which structural transition from 2D to 3D occurs. This, however, is a challenging task due to the complexity of these systems and the existence of a large number of isomers. Such 2D-to-3D structural transition is also strongly affected by the charges of boron clusters. For cationic boron clusters (B n + ), the largest planar or quasi-planar structure was established for n=15, and the transition from planar to cylindrical structure takes place for B 16 + [16]. Combining experiment (photoelectron spectroscopy) with computational studies (global minimum search), Kiran et al [17]found that the neutral B 20 cluster undergoes a 2D-to-3D structural transition, resulting in formation of a stable double-ring tubular structure with a diameter of 5.2 Å (Figure 1). The tubular structure was considered as the embryo of the thinnest single-walled boron nanotubes.However, the upper limit for the B n − anionic clusters still remains an open question. Through a joint study of photoelectron spectroscopy and ab initio computatio...

show abstract

“…Structure I is the GM of the B 36 cluster, [17][18][19] which features ideal inner and outer BDR ribbons. It also has ac haracteristic hexagonal hole [20,21,[23][24][25][26][27][28] at the center.…”

Section: Computationaldetailsmentioning

confidence: 99%

“…Consequently,w eb elieve the exact nature of bonding in the B 36 clusterh as remained elusive, despite prior computational works. [17][18][19] Interestingly,L iu et al recently raised aq uestion with regard to bonding and energetics in the B 36 cluster: [19] why does the hexagonal hole prefer to be located atacentral position?T ot he best of our knowledge,this fundamental question is still unanswered.…”

Section: Introductionmentioning

confidence: 99%

Nature of Bonding in Bowl‐Like B₃₆ Cluster Revisited: Concentric (6π+18π) Double Aromaticity and Reason for the Preference of a Hexagonal Hole in a Central Location

You

Wang

et al. 2018

Chemistry An Asian Journal

View full text Add to dashboard Cite

The bowl-shaped C B cluster with a central hexagon hole is considered an ideal molecular model for low-dimensional boron-based nanosystems. Owing to the electron deficiency of boron, chemical bonding in the B cluster is intriguing, complicated, and has remained elusive despite a couple of papers in the literature. Herein, a bonding analysis is given through canonical molecular orbitals (CMOs) and adaptive natural density partitioning (AdNDP), further aided by natural bond orbital (NBO) analysis and orbital composition calculations. The concerted computational data establish the idea of concentric double π aromaticity for the B cluster, with inner 6π and outer 18π electron counting, which both conform to the (4n+2) Hückel rule. The updated bonding picture differs from existing knowledge of the system. A refined bonding model is also proposed for coronene, of which the B cluster is an inorganic analogue. It is further shown that concentric double π aromaticity in the B cluster is retained and spatially fixed, irrespective of the migration of the hexagonal hole; the latter process changes the system energetically. The hexagonal hole is a destabilizing factor for σ/π CMOs. The central hexagon hole affects substantially fewer CMOs, thus making the bowl-shaped C B cluster the global minimum.

show abstract

Understanding the Central Location of a Hexagonal Hole in a B₃₆ Cluster

Cited by 8 publications

References 37 publications

B₃₃^– and B₃₄^–: Aromatic Planar Boron Clusters with a Hexagonal Vacancy

B₃₃^– and B₃₄^–: Aromatic Planar Boron Clusters with a Hexagonal Vacancy

Geometries and Electronic Structures of Boron Clusters: Planar Structures and All-boron Fullerenes

Nature of Bonding in Bowl‐Like B₃₆ Cluster Revisited: Concentric (6π+18π) Double Aromaticity and Reason for the Preference of a Hexagonal Hole in a Central Location

Contact Info

Product

Resources

About

Understanding the Central Location of a Hexagonal Hole in a B36 Cluster

Cited by 8 publications

References 37 publications

B33– and B34–: Aromatic Planar Boron Clusters with a Hexagonal Vacancy

B33– and B34–: Aromatic Planar Boron Clusters with a Hexagonal Vacancy

Geometries and Electronic Structures of Boron Clusters: Planar Structures and All-boron Fullerenes

Nature of Bonding in Bowl‐Like B36 Cluster Revisited: Concentric (6π+18π) Double Aromaticity and Reason for the Preference of a Hexagonal Hole in a Central Location

Contact Info

Product

Resources

About

Understanding the Central Location of a Hexagonal Hole in a B₃₆ Cluster

B₃₃^– and B₃₄^–: Aromatic Planar Boron Clusters with a Hexagonal Vacancy

B₃₃^– and B₃₄^–: Aromatic Planar Boron Clusters with a Hexagonal Vacancy

Nature of Bonding in Bowl‐Like B₃₆ Cluster Revisited: Concentric (6π+18π) Double Aromaticity and Reason for the Preference of a Hexagonal Hole in a Central Location