Chemical Bonding and Dynamic Structural Fluxionality of a Boron-Based B<sub>8</sub>Al<sub>3</sub><sup>+</sup> Cluster

We studied the boron-based composite cluster B<sub>8</sub>Al<sub>3</sub><sup>+</sup> doped with Al atoms. The global minimum structure of the B<sub>8</sub>Al<sub>3</sub><sup>+</sup> cluster is a three-layer structure, consisting...

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Main Authors: Shu-Juan Gao, Tan-Lai Yu
Format: Article
Language:English
Published: MDPI AG 2024-12-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/29/24/5961
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author Shu-Juan Gao
Tan-Lai Yu
author_facet Shu-Juan Gao
Tan-Lai Yu
author_sort Shu-Juan Gao
collection DOAJ
description We studied the boron-based composite cluster B<sub>8</sub>Al<sub>3</sub><sup>+</sup> doped with Al atoms. The global minimum structure of the B<sub>8</sub>Al<sub>3</sub><sup>+</sup> cluster is a three-layer structure, consisting of three parts: an Al<sub>2</sub> unit, a B<sub>8</sub> ring and an isolated Al atom. Charge calculations analysis shows that the cluster can be expressed as [Al]<sup>+</sup>[B<sub>8</sub>]<sup>2−</sup>[Al<sub>2</sub>]<sup>2+</sup>, has 6π/6σ double aromaticity and follows the (4<i>n</i>+2) Hückel rule. Born–Oppenheimer molecular dynamics (BOMD) simulation shows that the B<sub>8</sub>Al<sub>3</sub><sup>+</sup> cluster has dynamic fluxionality properties. Remarkably, at the single-point coupled cluster singles, doubles and triples (CCSD(T)) level, the energy barrier for intramolecular rotation is merely 0.19 kcal mol<sup>−1</sup>. [B<sub>8</sub>]<sup>2−</sup> molecular wheels have magical 6π/6σ double aromaticity properties, providing a continuous cloud of delocalized electrons, which is a key factor in the dynamic fluxionality of the cluster. The B<sub>8</sub>Al<sub>3</sub><sup>+</sup> cluster provides a new example of dynamic structural fluxionality in molecular systems.
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spelling doaj-art-ae7c71a1e15f47fd9abf42e6ccfe72092024-12-27T14:42:47ZengMDPI AGMolecules1420-30492024-12-012924596110.3390/molecules29245961Chemical Bonding and Dynamic Structural Fluxionality of a Boron-Based B<sub>8</sub>Al<sub>3</sub><sup>+</sup> ClusterShu-Juan Gao0Tan-Lai Yu1Department of Chemical and Materials Engineering, Lyuliang University, Lishi 033001, ChinaDepartment of Chemical and Materials Engineering, Lyuliang University, Lishi 033001, ChinaWe studied the boron-based composite cluster B<sub>8</sub>Al<sub>3</sub><sup>+</sup> doped with Al atoms. The global minimum structure of the B<sub>8</sub>Al<sub>3</sub><sup>+</sup> cluster is a three-layer structure, consisting of three parts: an Al<sub>2</sub> unit, a B<sub>8</sub> ring and an isolated Al atom. Charge calculations analysis shows that the cluster can be expressed as [Al]<sup>+</sup>[B<sub>8</sub>]<sup>2−</sup>[Al<sub>2</sub>]<sup>2+</sup>, has 6π/6σ double aromaticity and follows the (4<i>n</i>+2) Hückel rule. Born–Oppenheimer molecular dynamics (BOMD) simulation shows that the B<sub>8</sub>Al<sub>3</sub><sup>+</sup> cluster has dynamic fluxionality properties. Remarkably, at the single-point coupled cluster singles, doubles and triples (CCSD(T)) level, the energy barrier for intramolecular rotation is merely 0.19 kcal mol<sup>−1</sup>. [B<sub>8</sub>]<sup>2−</sup> molecular wheels have magical 6π/6σ double aromaticity properties, providing a continuous cloud of delocalized electrons, which is a key factor in the dynamic fluxionality of the cluster. The B<sub>8</sub>Al<sub>3</sub><sup>+</sup> cluster provides a new example of dynamic structural fluxionality in molecular systems.https://www.mdpi.com/1420-3049/29/24/5961dual π/σ aromaticitydynamic structural fluxionalitychemical bondingtheoretical chemistry
spellingShingle Shu-Juan Gao
Tan-Lai Yu
Chemical Bonding and Dynamic Structural Fluxionality of a Boron-Based B<sub>8</sub>Al<sub>3</sub><sup>+</sup> Cluster
Molecules
dual π/σ aromaticity
dynamic structural fluxionality
chemical bonding
theoretical chemistry
title Chemical Bonding and Dynamic Structural Fluxionality of a Boron-Based B<sub>8</sub>Al<sub>3</sub><sup>+</sup> Cluster
title_full Chemical Bonding and Dynamic Structural Fluxionality of a Boron-Based B<sub>8</sub>Al<sub>3</sub><sup>+</sup> Cluster
title_fullStr Chemical Bonding and Dynamic Structural Fluxionality of a Boron-Based B<sub>8</sub>Al<sub>3</sub><sup>+</sup> Cluster
title_full_unstemmed Chemical Bonding and Dynamic Structural Fluxionality of a Boron-Based B<sub>8</sub>Al<sub>3</sub><sup>+</sup> Cluster
title_short Chemical Bonding and Dynamic Structural Fluxionality of a Boron-Based B<sub>8</sub>Al<sub>3</sub><sup>+</sup> Cluster
title_sort chemical bonding and dynamic structural fluxionality of a boron based b sub 8 sub al sub 3 sub sup sup cluster
topic dual π/σ aromaticity
dynamic structural fluxionality
chemical bonding
theoretical chemistry
url https://www.mdpi.com/1420-3049/29/24/5961
work_keys_str_mv AT shujuangao chemicalbondinganddynamicstructuralfluxionalityofaboronbasedbsub8subalsub3subsupsupcluster
AT tanlaiyu chemicalbondinganddynamicstructuralfluxionalityofaboronbasedbsub8subalsub3subsupsupcluster