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Chemical Bonding and Dynamic Structural Fluxionality of a Boron-Based Na(5)B(7) Sandwich Cluster

Doping alkali metals into boron clusters can effectively compensate for the intrinsic electron deficiency of boron and lead to interesting boron-based binary clusters, owing to the small electronegativity of the former elements. We report on the computational design of a three-layered sandwich clust...

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Autores principales: Han, Peng-Fei, Wang, Ying-Jin, Feng, Lin-Yan, Gao, Shu-Juan, Sun, Qiang, Zhai, Hua-Jin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10096537/
https://www.ncbi.nlm.nih.gov/pubmed/37050038
http://dx.doi.org/10.3390/molecules28073276
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author Han, Peng-Fei
Wang, Ying-Jin
Feng, Lin-Yan
Gao, Shu-Juan
Sun, Qiang
Zhai, Hua-Jin
author_facet Han, Peng-Fei
Wang, Ying-Jin
Feng, Lin-Yan
Gao, Shu-Juan
Sun, Qiang
Zhai, Hua-Jin
author_sort Han, Peng-Fei
collection PubMed
description Doping alkali metals into boron clusters can effectively compensate for the intrinsic electron deficiency of boron and lead to interesting boron-based binary clusters, owing to the small electronegativity of the former elements. We report on the computational design of a three-layered sandwich cluster, Na(5)B(7), on the basis of global-minimum (GM) searches and electronic structure calculations. It is shown that the Na(5)B(7) cluster can be described as a charge-transfer complex: [Na(4)](2+)[B(7)](3−)[Na](+). In this sandwich cluster, the [B(7)](3−) core assumes a molecular wheel in shape and features in-plane hexagonal coordination. The magic 6π/6σ double aromaticity underlies the stability of the [B(7)](3−) molecular wheel, following the (4n + 2) Hückel rule. The tetrahedral Na(4) ligand in the sandwich has a [Na(4)](2+) charge-state, which is the simplest example of three-dimensional aromaticity, spherical aromaticity, or superatom. Its 2σ electron counting renders σ aromaticity for the ligand. Overall, the sandwich cluster has three-fold 6π/6σ/2σ aromaticity. Molecular dynamics simulation shows that the sandwich cluster is dynamically fluxional even at room temperature, with a negligible energy barrier for intramolecular twisting between the B(7) wheel and the Na(4) ligand. The Na(5)B(7) cluster offers a new example for dynamic structural fluxionality in molecular systems.
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spelling pubmed-100965372023-04-13 Chemical Bonding and Dynamic Structural Fluxionality of a Boron-Based Na(5)B(7) Sandwich Cluster Han, Peng-Fei Wang, Ying-Jin Feng, Lin-Yan Gao, Shu-Juan Sun, Qiang Zhai, Hua-Jin Molecules Article Doping alkali metals into boron clusters can effectively compensate for the intrinsic electron deficiency of boron and lead to interesting boron-based binary clusters, owing to the small electronegativity of the former elements. We report on the computational design of a three-layered sandwich cluster, Na(5)B(7), on the basis of global-minimum (GM) searches and electronic structure calculations. It is shown that the Na(5)B(7) cluster can be described as a charge-transfer complex: [Na(4)](2+)[B(7)](3−)[Na](+). In this sandwich cluster, the [B(7)](3−) core assumes a molecular wheel in shape and features in-plane hexagonal coordination. The magic 6π/6σ double aromaticity underlies the stability of the [B(7)](3−) molecular wheel, following the (4n + 2) Hückel rule. The tetrahedral Na(4) ligand in the sandwich has a [Na(4)](2+) charge-state, which is the simplest example of three-dimensional aromaticity, spherical aromaticity, or superatom. Its 2σ electron counting renders σ aromaticity for the ligand. Overall, the sandwich cluster has three-fold 6π/6σ/2σ aromaticity. Molecular dynamics simulation shows that the sandwich cluster is dynamically fluxional even at room temperature, with a negligible energy barrier for intramolecular twisting between the B(7) wheel and the Na(4) ligand. The Na(5)B(7) cluster offers a new example for dynamic structural fluxionality in molecular systems. MDPI 2023-04-06 /pmc/articles/PMC10096537/ /pubmed/37050038 http://dx.doi.org/10.3390/molecules28073276 Text en © 2023 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Han, Peng-Fei
Wang, Ying-Jin
Feng, Lin-Yan
Gao, Shu-Juan
Sun, Qiang
Zhai, Hua-Jin
Chemical Bonding and Dynamic Structural Fluxionality of a Boron-Based Na(5)B(7) Sandwich Cluster
title Chemical Bonding and Dynamic Structural Fluxionality of a Boron-Based Na(5)B(7) Sandwich Cluster
title_full Chemical Bonding and Dynamic Structural Fluxionality of a Boron-Based Na(5)B(7) Sandwich Cluster
title_fullStr Chemical Bonding and Dynamic Structural Fluxionality of a Boron-Based Na(5)B(7) Sandwich Cluster
title_full_unstemmed Chemical Bonding and Dynamic Structural Fluxionality of a Boron-Based Na(5)B(7) Sandwich Cluster
title_short Chemical Bonding and Dynamic Structural Fluxionality of a Boron-Based Na(5)B(7) Sandwich Cluster
title_sort chemical bonding and dynamic structural fluxionality of a boron-based na(5)b(7) sandwich cluster
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10096537/
https://www.ncbi.nlm.nih.gov/pubmed/37050038
http://dx.doi.org/10.3390/molecules28073276
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