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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding
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An Unprecedented Interconversion Between Non-covalent and Covalent Interactions Driven by Halogen Bonding.

Xiankai Jiang1, Junjian Miao2, Yi Gao3

  • 1School of Sciences, Changzhou Institute of Technology, Changzhou, 213032, P. R. China.

Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry
|March 10, 2022
PubMed
Summary

Researchers discovered a transformation between covalent and noncovalent forces in nitrogen triiodide (NI₃) via halogen bonding. This interconversion, observed in NI₃ oligomers, offers insights into halogen bonding and explosive properties.

Keywords:
NI3covalent bondshalogen bondslocalized molecular orbitalsnon-covalent interactions

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Area of Science:

  • Chemical Physics
  • Materials Science
  • Computational Chemistry

Background:

  • The transition between covalent and noncovalent interactions is not fully understood.
  • Nitrogen triiodide (NI₃) is known for its explosive nature, but the underlying mechanisms are unclear.

Purpose of the Study:

  • To investigate the spontaneous interconversion between covalent and noncovalent forces.
  • To explore the role of halogen bonding in this transformation using NI₃ as a model system.
  • To understand the relationship between this interconversion and the explosive properties of NI₃.

Main Methods:

  • Computational modeling of NI₃ dimers and oligomers (5- to 30-mers).
  • Analysis of interaction strengths, bond distances, and Electron Localization Function (ELF).
  • Molecular orbital analyses to understand electronic structure contributions.

Main Results:

  • A strong halogen bond was identified in the NI₃ dimer with an interaction strength of 7.01 kcal/mol.
  • The interconversion between covalent and noncovalent characteristics was observed to occur gradually around the 26-mer of NI₃.
  • Strong mixing of frontier molecular orbitals suggests a basis for the observed interconversion.

Conclusions:

  • Halogen bonding facilitates a unique transformation between covalent and noncovalent interactions in NI₃.
  • The interconversion is a gradual process, not abrupt, occurring in larger NI₃ assemblies.
  • Findings provide new perspectives on halogen bonding and the high explosivity of NI₃-based compounds.