Quantum rules for planar boron nanoclusters

Arvanitidis, Athanasios G.; Tai, Truong Ba; Nguyen, Minh Tho; Ceulemans, Arnout

doi:10.1039/c4cp02323d

Cited by 35 publications

(28 citation statements)

References 32 publications

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“…First of all, since all clusters are quasi‐planar or exactly planar, the valence orbitals can be partitioned in a π and a σ shell. As we have shown before, the π‐bonding is of multicenter character and follows the simple particle in an elongated box model B7− has only two π bonds, and, therefore, is anti‐aromatic as far as π‐aromaticity is concerned.…”

Section: Resultsmentioning

confidence: 59%

Valence bonds in elongated boron clusters

Arvanitidis

Lim

Havenith

et al. 2018

Int J of Quantum Chemistry

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A well-defined class of planar or quasi-planar elongated boron clusters, of type B q2 713n , serves as a basis to identify the valence bond picture of delocalized boron networks. The origin of the series is the B 2 7 cluster, which exhibits r-aromaticity. The cluster generating step is the repetitive expansion by three boron atoms in the direction of elongation. Specific electron counting rules are obtained for p-bonding, peripheral r-bonding and multicenter inner r-bonding. A valence bond structure is introduced which explains the remarkable regularity in the bonding pattern. The analysis supports 4c-2e bonds as an alternative to the common 3c-2e bonds. The results are validated by symmetry induction and ab initio calculations. K E Y W O R D S boron clusters, computational chemistry, induction method, multicenter bonding 1 | I N TR ODU C TI ONThe recent literature reports on a wide variety of planar and bowl shaped boron clusters. Proposed structures are usually based on theoretical calculations, but for some cases structures could be confirmed by photoelectron or infrared spectroscopy [1] on clusters produced by laser evaporation. [2][3][4] A further special feature of some clusters which are shaped like two concentric rings is the almost barrierless rotatory motion of the inner ring with respect to the outer ring. [5] This motion has been compared to a Wankel motor at the molecular scale. [6] In view of the rich variety of shapes and properties, which challenges accepted concepts of chemical bonding, boron is said to be the new carbon. As opposed to carbon, it is known to adopt multicenter bonds which have to be accomodated in a proper theoretical scheme. [7][8][9] To build a consistent valence bond picture that would apply to all these clusters, a gradual approach is required based on a well-defined set of structures. For this, we chose the particular family of the so-called elongated boron clusters. The aim is to obtain a set of rules that rationalize the electronic structure calculations on a series of structures extending from B 2 7 to B 22 28 . [10][11][12][13][14][15][16][17][18] Int J Quantum Chem. 2018;118:e25575.

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Section: Resultsmentioning

confidence: 59%

Valence bonds in elongated boron clusters

Arvanitidis

Lim

Havenith

et al. 2018

Int J of Quantum Chemistry

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“…12 However, the Hückel electron count cannot be applied to many boron clusters having planar and tubular shapes. 15,34,35,36 The simple models of a particle moving in a box associated with a specific cluster geometry provide us with an excellent interpretation not only for their electronic structure but also for their aromatic character. As a matter of fact, for tubular clusters including B20, B22, B24, B26, B27 + and B42, the model of a particle moving in hollow cylinder excellently reproduces the shapes and energy levels of the MOs of these clusters, and thereby establishing some novel electron counts.…”

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confidence: 99%

“…In considering the model of a particle moving in a circular disk, the concept of disk aromaticity has been proposed and can successfully rationalize the stability for concentric ("ringin-ring") planar boron clusters including B18 2-, B19and B20 2-. 35,36 Some quantum rules have been put forward for the planar Bn up to size n = 20. 36,37 The high stability of bowl-shaped clusters such as B30, B32, B36 and B42 can also be rationalized in terms of the disk aromacity concept.…”

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Formation of the quasi-planar B₅₀boron cluster: topological path from B₁₀and disk aromaticity

Pham

Muya

Buendía

et al. 2019

Phys. Chem. Chem. Phys.

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“…9 The bowl-shaped B 30 , B 32 and B 36 10,11,12 and quasi-planar B 35 13 clusters can serve as building blocks to form various boron sheets. 16,17,18 The boron atom has the capacity to form strong covalent bonds not only with itself but also with many other elements. Let us note that in both B 38 and B 40 sizes, the fullerenes 10,15 and the quasi-planar isomes 9 are quite close in energy content.…”

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Effects of bimetallic doping on small cyclic and tubular boron clusters: B₇M₂and B₁₄M₂structures with M = Fe, Co

Pham

Nguyen

2015

Phys. Chem. Chem. Phys.

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Using density functional theory with the TPSSh functional and the 6-311+G(d) basis set, we extensively searched for the global minima of two metallic atoms doped boron clusters B6M2, B7M2, B12M2 and B14M2 with transition metal element M being Co and Fe. Structural identifications reveal that B7Co2, B7Fe2 and B7CoFe clusters have global minima in a B-cyclic motif, in which a perfectly planar B7 is coordinated with two metallic atoms placed along the C7 axis. The B6 cluster is too small to form a cycle with the presence of two metals. Similarly, the B12 cluster is not large enough to stabilize the metallic dimer within a double ring 2 × B6 tube. The doped B14M2 clusters including B14Co2, B14Fe2 and B14CoFe have a double ring 2 × B7 tubular shape in which one metal atom is encapsulated by the B14 tube and the other is located at an exposed position. Dissociation energies demonstrate that while bimetallic cyclic cluster B7M2 prefers a fragmentation channel that generates the B7 global minimum plus metallic dimer, the tubular structure B14M2 tends to dissociate giving a bimetallic cyclic structure B7M2 and a B@B6 cluster. The enhanced stability of the bimetallic doped boron clusters considered can be understood from the stabilizing interactions between the anti-bonding MOs of metal-metal dimers and the levels of a disk aromatic configuration (for bimetallic cyclic structures), or the eigenstates of the B14 tubular form (in case of bimetallic tubular structure).

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Quantum rules for planar boron nanoclusters

Cited by 35 publications

References 32 publications

Valence bonds in elongated boron clusters

Valence bonds in elongated boron clusters

Formation of the quasi-planar B₅₀boron cluster: topological path from B₁₀and disk aromaticity

Effects of bimetallic doping on small cyclic and tubular boron clusters: B₇M₂and B₁₄M₂structures with M = Fe, Co

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Quantum rules for planar boron nanoclusters

Cited by 35 publications

References 32 publications

Valence bonds in elongated boron clusters

Valence bonds in elongated boron clusters

Formation of the quasi-planar B50boron cluster: topological path from B10and disk aromaticity

Effects of bimetallic doping on small cyclic and tubular boron clusters: B7M2and B14M2structures with M = Fe, Co

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Formation of the quasi-planar B₅₀boron cluster: topological path from B₁₀and disk aromaticity

Effects of bimetallic doping on small cyclic and tubular boron clusters: B₇M₂and B₁₄M₂structures with M = Fe, Co