Jump to main content
Jump to site search

Issue 40, 2016
Previous Article Next Article

Cation–cation and anion–anion complexes stabilized by halogen bonds

Author affiliations

Abstract

Stable minima showing halogen bonds between charged molecules with the same sign have been explored by means of theoretical calculations. The dissociation transition states and their corresponding barriers have also been characterized. In all cases, the results indicate that the complexes are thermodynamically unstable but kinetically stable with respect to the isolated monomers in gas phase. A corrected binding energy profile by removing the charge–charge repulsion of the monomers shows a profile similar to the one observed for the dissociation of analogous neutral systems. The nature of the interaction in the minima and TSs has been analyzed using the symmetry adapted perturbation theory (SAPT) method. The results indicate the presence of local favorable electrostatic interactions in the minima that vanish in the TSs. Natural bond orbital (NBO) and “atoms-in-molecules” (AIM) theories were used to analyze the complexes, obtaining good correlations between Laplacian and electron density values with both bond distances and charge-transfer energy contributions E(2). The largest E(2) orbital interaction energies for cation–cation and anion–anion complexes are 561.2 and 197.9 kJ mol−1, respectively.

Graphical abstract: Cation–cation and anion–anion complexes stabilized by halogen bonds

Back to tab navigation

Supplementary files

Publication details

The article was received on 27 May 2016, accepted on 09 Sep 2016 and first published on 09 Sep 2016


Article type: Paper
DOI: 10.1039/C6CP03662G
Citation: Phys. Chem. Chem. Phys., 2016,18, 27939-27950
  • Open access: Creative Commons BY-NC license
  •   Request permissions

    Cation–cation and anion–anion complexes stabilized by halogen bonds

    D. Quiñonero, I. Alkorta and J. Elguero, Phys. Chem. Chem. Phys., 2016, 18, 27939
    DOI: 10.1039/C6CP03662G

    This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material and it is not used for commercial purposes.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements