Next Article in Journal
Photocracking Silica: Tuning the Plasmonic Photothermal Degradation of Mesoporous Silica Encapsulating Gold Nanoparticles for Cargo Release
Previous Article in Journal
Revealing the Nature of Chemical Bonding in an ALn2Ag3Te5-Type Alkaline-Metal (A) Lanthanide (Ln) Silver Telluride
Previous Article in Special Issue
A Continuum from Halogen Bonds to Covalent Bonds: Where Do λ3 Iodanes Fit?
Article Menu
Issue 6 (June) cover image

Export Article

Open AccessArticle

σ-Holes vs. Buildups of Electronic Density on the Extensions of Bonds to Halogen Atoms

Department of Chemistry, University of New Orleans, New Orleans, LA 70148, USA
*
Author to whom correspondence should be addressed.
Inorganics 2019, 7(6), 71; https://doi.org/10.3390/inorganics7060071
Received: 13 May 2019 / Revised: 28 May 2019 / Accepted: 31 May 2019 / Published: 6 June 2019
(This article belongs to the Special Issue Halogen Bonding: Fundamentals and Applications)
  |  
PDF [735 KB, uploaded 6 June 2019]
  |  

Abstract

Our discussion focuses upon three possible features that a bonded halogen atom may exhibit on its outer side, on the extension of the bond. These are (1) a region of lower electronic density (a σ-hole) accompanied by a positive electrostatic potential with a local maximum, (2) a region of lower electronic density (a σ-hole) accompanied by a negative electrostatic potential that also has a local maximum, and (3) a buildup of electronic density accompanied by a negative electrostatic potential that has a local minimum. In the last case, there is no σ-hole. We show that for diatomic halides and halogen-substituted hydrides, the signs and magnitudes of these maxima and minima can be expressed quite well in terms of the differences in the electronegativities of the halogen atoms and their bonding partners, and the polarizabilities of both. We suggest that the buildup of electronic density and absence of a σ-hole on the extension of the bond to the halogen may be an operational indication of ionicity. View Full-Text
Keywords: halogen bonding; σ-holes; positive and negative electrostatic potentials; electronic densities; ionicity halogen bonding; σ-holes; positive and negative electrostatic potentials; electronic densities; ionicity
Figures

Figure 1

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).
SciFeed

Share & Cite This Article

MDPI and ACS Style

Politzer, P.; Murray, J.S. σ-Holes vs. Buildups of Electronic Density on the Extensions of Bonds to Halogen Atoms. Inorganics 2019, 7, 71.

Show more citation formats Show less citations formats

Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Related Articles

Article Metrics

Article Access Statistics

1

Comments

[Return to top]
Inorganics EISSN 2304-6740 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top