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Theoretical investigation of substituent effects on the relative stabilities and electronic structure of [BnXn]2− clusters

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Abstract

In this study, we provide a theoretical evaluation of relative stabilities and electronic structure for [BnXn]2− clusters (n = 10, 12, 13, 14, 15, 16). Structural and electronic characteristics of [BnXn]2− clusters are examined by comparison with the [B12X12]2− counterparts with a focus on the substituent effects (X = H, F, Cl, Br, CN, BO, OH, NH2) on the electronic structure, electron detachment energies, formation enthalpies, and charge distributions. For the electronic structure and electron detachment energies, substituent effects on boron clusters are shown to follow a very similar trend to the mesomeric and inductive effects (± M and ± I) of π-conjugated systems, and the most stable derivatives in terms of HOMO/LUMO and electron detachment energies are calculated for CN and BO substituents due to strong -M effects. In the case of formation enthalpies for larger boron clusters (n ≥ 13), the icosahedral barrier is shown to increase with the halogen and CN substitution, whereas it is possible to reduce the icosahedral barrier for the cases of X = OH and NH2. It is shown that this reduction results from destabilizing the [B12X12]2− cluster with electronic (+ M) and symmetry effects induced by OH and NH2 ligands.

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All relevant data are available in the electronic supplementary information.

Code availability

Gaussian 09 Revision A.02 is used for all the calculations in this work. Gaussview 5.0 is used for the visualization and generation of figures in the article.

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Acknowledgements

We would like to thank Prof. Hakan Usta for carefully reading the manuscript and their valuable recommendations. We are indebted to Abdullah Gül University for making the facilities of the High-Performance Computing (HPC) center available for our computational work.

Funding

This work was supported by Research Fund of Abdullah Gül University (Project Number: FDK-2018–122).

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Authors and Affiliations

  1. Department of Nanotechnology Engineering, Abdullah Gül University, Kayseri, Turkey

    Duygu Tahaoğlu, Fahri Alkan & Murat Durandurdu

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  1. Duygu Tahaoğlu
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  2. Fahri Alkan
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  3. Murat Durandurdu
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Contributions

DT, FA, and MD conceived the idea and planned the computations in this study. DT ran the most of the computations and wrote the first draft for this manuscript. FA supervised the project. MD edited and reviewed the manuscript prior to submission. All authors approved the contents of this manuscript.

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Correspondence to Fahri Alkan.

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Tahaoğlu, D., Alkan, F. & Durandurdu, M. Theoretical investigation of substituent effects on the relative stabilities and electronic structure of [BnXn]2− clusters. J Mol Model 27, 365 (2021). https://doi.org/10.1007/s00894-021-04980-1

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