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Updated: May 12, 2026

From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding
06:44

From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding

Published on: March 24, 2018

Are halogen bonded structures electrostatically driven?

Anthony J Stone1

  • 1University Chemical Laboratory, University of Cambridge, Cambridge, UK. ajs1@cam.ac.uk

Journal of the American Chemical Society
|April 16, 2013
PubMed
Summary
This summary is machine-generated.

Halogen bonds are often considered electrostatic, but analysis reveals exchange-repulsion, not just electrostatics, dictates their linear geometry. This finding refines our understanding of these important chemical interactions.

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Area of Science:

  • Chemical Physics
  • Molecular Interactions
  • Computational Chemistry

Background:

  • Halogen-bonded complexes (B···XY) are traditionally viewed as primarily electrostatic interactions.
  • Their structural similarities to hydrogen bonds reinforce this electrostatic perspective.

Purpose of the Study:

  • To investigate the driving forces behind the geometry of halogen-bonded complexes.
  • To determine the precise contributions of different energy components to halogen bond formation and structure.

Main Methods:

  • Utilized symmetry-adapted perturbation theory (SAPT) to analyze the components of the binding energy.
  • Examined the energetic contributions to the overall structure of halogen-bonded systems.

Main Results:

  • Electrostatic energy is typically the dominant contribution to the binding energy in halogen bonds.
  • However, electrostatic forces alone do not fully determine the observed geometries.
  • The pronounced linearity of the B···XY bond is primarily driven by exchange-repulsion effects.

Conclusions:

  • The traditional electrostatic model for halogen bonds is incomplete.
  • Exchange-repulsion plays a crucial role in dictating the geometric preferences, particularly linearity.
  • A more nuanced understanding of halogen bonding requires considering both electrostatic and repulsive forces.