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Molecular triskelions: structure and bonding in the perhalogenated analogues of boric acid, X3BO3 (X=F, Cl, Br, I)

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Abstract

Using density functional theory calculations, we investigate the geometries and electronic structures of the perhalogenated derivatives of boric acid, X3BO3 (with X = halogen). These molecules in their low-energy states are C3h symmetric with a shape that resembles a triskelion, an ancient symbol that appears inside the flags and coat of arms of countries, regions, and cities throughout Europe. The molecular triskelions can form polar complexes with ammonia which are stabilized by a dative bond between nitrogen and boron, while a second type of adducts arises from the halogen bonding between nitrogen and the terminal halogen atom. By virtue of their different HOMO–LUMO gaps, the molecular triskelions and their complexes with ammonia might provide novel bulk materials where the band gap can be tuned simply by changing the type of halogen bonded to the BO3 moiety.

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Acknowledgments

I wish to thank Professor István Hargittai for inviting me to contribute to this special issue of Structural Chemistry dedicated to Alan Mackay’s 90th birthday and for stimulating discussions about symmetry. Also, the useful suggestions of anonymous reviewers are gratefully acknowledged. This work is supported by the Department of Applied Chemistry of the Graduate School of Engineering (Tohoku University) and by the Japan Society for the Promotion of Science (JSPS) “Grants-in-Aid for Scientific Research” (Kakenhi-C) Nr. 15K05580.

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Correspondence to Fabio Pichierri.

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This article is dedicated to Alan Mackay’s 90th birthday.

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Pichierri, F. Molecular triskelions: structure and bonding in the perhalogenated analogues of boric acid, X3BO3 (X=F, Cl, Br, I). Struct Chem 28, 213–223 (2017). https://doi.org/10.1007/s11224-016-0835-5

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Keywords

  • Boron chemistry
  • Halogen bonding
  • Computational prediction
  • Quantum chemistry
  • DFT