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Inorganics
Special Issues
Halogen Bonding: Fundamentals and Applications
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Halogen Bonding: Fundamentals and Applications

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Coordination Chemistry".

Deadline for manuscript submissions: closed (30 September 2019) | Viewed by 30831

Special Issue Editors

Prof. Dr. Nathan I. Hammer

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Guest Editor
Department of Chemistry and Biochemistry, University of Mississippi, University, MS 38677, USA
Interests: spectroscopy; noncovalent interactions; hydrogen bonding; computational chemistry
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Gregory Tschumper

E-Mail Website
Guest Editor
Department of Chemistry and Biochemistry, University of Mississippi, University, MS 38677, USA
Interests: computational chemistry; noncovalent interactions; hydrogen bonding
Special Issues, Collections and Topics in MDPI journals
Dr. Davita L. Watkins

E-Mail Website
Guest Editor
Department of Chemistry and Biochemistry, University of Mississippi, University, MS, USA
Interests: organic and materials chemistry; supramolecular chemistry; organic electronics; noncovalent interactions; semiconductors; biomaterials; optical electronic behavior; smart materials; conjugated nanostructures

Special Issue Information

Dear Colleagues,

Although halogen bonding was not widely appreciated in the chemical sciences until the last two or three decades, evidence for the influence of this inter- and intra-molecular force on the solid-state arrangement of halogen-containing compounds can be traced back at least two centuries. Halogen bonds, analogous to the ubiquitous hydrogen bond, are noncovalent interactions between an electrophilic region of a halogen atom and a nucleophilic region of a molecular entity (e.g., electron-pair-donating heteroatoms or π-system). The phenomenon originates from the anisotropic distribution of electron density (i.e., σ-hole) around the halogen atom which affords a highly directional, tunable interaction. A reemergence of this special class of σ-hole bonding has recently attracted special attention. In recent years, ingenious design strategies, computational analyses, and structural models have afforded progression beyond the field of crystal engineering and pharmaceutics to material science and nanotechnology. 

Inspired by the great potential of halogen bonding in supramolecular complexes and bottom-up approaches, it is the intention of this Special Issue to provide an overview on several aspects of halogen bonding in fundamental and applied science. This Special Issue “Halogen Bonding: Fundamentals and Applications” in Inorganics will take stock of the efforts and results of the many groups that have made evident progress in the field. 

Prof. Dr. Nathan I. Hammer
Prof. Dr. Gregory Tschumper
Prof. Dr. Davita L. Watkins
Guest Editors

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Inorganics is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • halogen bonding
  • sigma-hole interactions
  • molecular recognition self-assembly
  • supramolecular structures
  • structure-property relationship
  • crystal engineering
  • Lewis base/acid
  • coordination chemistry
  • computational chemistry
  • supramolecular materials supramolecular chemistry
  • weak interactions
  • molecular devices molecular spectroscopy
  • vibrational spectroscopy
  • noncovalent interactions
  • charge-transfer complexes
  • intermolecular interactions

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Published Papers (6 papers)

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Research

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17 pages, 2069 KiB  
Article
A Raman Spectroscopic and Computational Study of New Aromatic Pyrimidine-Based Halogen Bond Acceptors
by April E. S. Hardin, Thomas L. Ellington, Suong T. Nguyen, Arnold L. Rheingold, Gregory S. Tschumper, Davita L. Watkins and Nathan I. Hammer
Inorganics 2019, 7(10), 119; https://doi.org/10.3390/inorganics7100119 - 2 Oct 2019
Cited by 6 | Viewed by 4161
Abstract
Two new aromatic pyrimidine-based derivatives designed specifically for halogen bond directed self-assembly are investigated through a combination of high-resolution Raman spectroscopy, X-ray crystallography, and computational quantum chemistry. The vibrational frequencies of these new molecular building blocks, pyrimidine capped with furan (PrmF) and thiophene [...] Read more.
Two new aromatic pyrimidine-based derivatives designed specifically for halogen bond directed self-assembly are investigated through a combination of high-resolution Raman spectroscopy, X-ray crystallography, and computational quantum chemistry. The vibrational frequencies of these new molecular building blocks, pyrimidine capped with furan (PrmF) and thiophene (PrmT), are compared to those previously assigned for pyrimidine (Prm). The modifications affect only a select few of the normal modes of Prm, most noticeably its signature ring breathing mode, ν1. Structural analyses afforded by X-ray crystallography, and computed interaction energies from density functional theory computations indicate that, although weak hydrogen bonding (C–H···O or C–H···N interactions) is present in these pyrimidine-based solid-state co-crystals, halogen bonding and π-stacking interactions play more dominant roles in driving their molecular-assembly. Full article
(This article belongs to the Special Issue Halogen Bonding: Fundamentals and Applications)
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11 pages, 735 KiB  
Article
σ-Holes vs. Buildups of Electronic Density on the Extensions of Bonds to Halogen Atoms
by Peter Politzer and Jane S. Murray
Inorganics 2019, 7(6), 71; https://doi.org/10.3390/inorganics7060071 - 6 Jun 2019
Cited by 3 | Viewed by 2691
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 [...] Read more.
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. Full article
(This article belongs to the Special Issue Halogen Bonding: Fundamentals and Applications)
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Figure 1

23 pages, 730 KiB  
Article
A Continuum from Halogen Bonds to Covalent Bonds: Where Do λ3 Iodanes Fit?
by Seth Yannacone, Vytor Oliveira, Niraj Verma and Elfi Kraka
Inorganics 2019, 7(4), 47; https://doi.org/10.3390/inorganics7040047 - 28 Mar 2019
Cited by 41 | Viewed by 5291
Abstract
The intrinsic bonding nature of λ 3 -iodanes was investigated to determine where its hypervalent bonds fit along the spectrum between halogen bonding and covalent bonding. Density functional theory with an augmented Dunning valence triple zeta basis set ( ω B97X-D/aug-cc-pVTZ) coupled with [...] Read more.
The intrinsic bonding nature of λ 3 -iodanes was investigated to determine where its hypervalent bonds fit along the spectrum between halogen bonding and covalent bonding. Density functional theory with an augmented Dunning valence triple zeta basis set ( ω B97X-D/aug-cc-pVTZ) coupled with vibrational spectroscopy was utilized to study a diverse set of 34 hypervalent iodine compounds. This level of theory was rationalized by comparing computational and experimental data for a small set of closely-related and well-studied iodine molecules and by a comparison with CCSD(T)/aug-cc-pVTZ results for a subset of the investigated iodine compounds. Axial bonds in λ 3 -iodanes fit between the three-center four-electron bond, as observed for the trihalide species IF 2 − and the covalent FI molecule. The equatorial bonds in λ 3 -iodanes are of a covalent nature. We explored how the equatorial ligand and axial substituents affect the chemical properties of λ 3 -iodanes by analyzing natural bond orbital charges, local vibrational modes, the covalent/electrostatic character, and the three-center four-electron bonding character. In summary, our results show for the first time that there is a smooth transition between halogen bonding → 3c–4e bonding in trihalides → 3c–4e bonding in hypervalent iodine compounds → covalent bonding, opening a manifold of new avenues for the design of hypervalent iodine compounds with specific properties. Full article
(This article belongs to the Special Issue Halogen Bonding: Fundamentals and Applications)
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14 pages, 3329 KiB  
Article
Non-Covalent Interactions Involving Alkaline-Earth Atoms and Lewis Bases B: An ab Initio Investigation of Beryllium and Magnesium Bonds, B···MR2 (M = Be or Mg, and R = H, F or CH3)
by Ibon Alkorta and Anthony C. Legon
Inorganics 2019, 7(3), 35; https://doi.org/10.3390/inorganics7030035 - 5 Mar 2019
Cited by 20 | Viewed by 3717
Abstract
Geometries, equilibrium dissociation energies (De), intermolecular stretching, and quadratic force constants (kσ) determined by ab initio calculations conducted at the CCSD(T)/aug-cc-pVTZ level of theory, with De obtained by using the complete basis set (CBS) extrapolation [CCSD(T)/CBS [...] Read more.
Geometries, equilibrium dissociation energies (De), intermolecular stretching, and quadratic force constants (kσ) determined by ab initio calculations conducted at the CCSD(T)/aug-cc-pVTZ level of theory, with De obtained by using the complete basis set (CBS) extrapolation [CCSD(T)/CBS energy], are presented for the B···BeR2 and B···MgR2 complexes, where B is one of the following Lewis bases: CO, H2S, PH3, HCN, H2O or NH3, and R is H, F or CH3. The BeR2 and MgR2 precursor molecules were shown to be linear and non-dipolar. The non-covalent intermolecular bond in the B···BeR2 complexes is shown to result from the interaction of the electrophilic band around the Be atom of BeR2 (as indicated by the molecular electrostatic potential surface) with non-bonding electron pairs of the base, B, and may be described as a beryllium bond by analogy with complexes such as B···CO2, which contain a tetrel bond. The conclusions for the B···MgR2 series are similar and a magnesium bond can be correspondingly invoked. The geometries established for B···BeR2 and B···MgR2 can be rationalized by a simple rule previously enunciated for tetrel-bonded complexes of the type B···CO2. It is also shown that the dissociation energy, De, is directly proportional to the force constant, kσ, in each B···MR2 series, but with a constant of proportionality different from that established for many hydrogen-bonded B···HX complexes and halogen-bonded B···XY complexes. The values of the electrophilicity, EA, determined from the De for B···BeR2 complexes for the individual Lewis acids, A, reveal the order A = BeF2 > BeH2 > Be(CH3)2—a result that is consistent with the −I and +I effects of F and CH3 relative to H. The conclusions for the MgR2 series are similar but, for a given R, they have smaller electrophilicities than those of the BeR2 series. A definition of alkaline-earth non-covalent bonds is presented. Full article
(This article belongs to the Special Issue Halogen Bonding: Fundamentals and Applications)
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18 pages, 1150 KiB  
Article
A Simple Model for Halogen Bond Interaction Energies
by Robert A. Shaw and J. Grant Hill
Inorganics 2019, 7(2), 19; https://doi.org/10.3390/inorganics7020019 - 10 Feb 2019
Cited by 9 | Viewed by 5038
Abstract
Halogen bonds are prevalent in many areas of chemistry, physics, and biology. We present a statistical model for the interaction energies of halogen-bonded systems at equilibrium based on high-accuracy ab initio benchmark calculations for a range of complexes. Remarkably, the resulting model requires [...] Read more.
Halogen bonds are prevalent in many areas of chemistry, physics, and biology. We present a statistical model for the interaction energies of halogen-bonded systems at equilibrium based on high-accuracy ab initio benchmark calculations for a range of complexes. Remarkably, the resulting model requires only two fitted parameters, X and B—one for each molecule—and optionally the equilibrium separation, R e , between them, taking the simple form E = X B / R e n . For n = 4 , it gives negligible root-mean-squared deviations of 0.14 and 0.28 kcal mol − 1 over separate fitting and validation data sets of 60 and 74 systems, respectively. The simple model is shown to outperform some of the best density functionals for non-covalent interactions, once parameters are available, at essentially zero computational cost. Additionally, we demonstrate how it can be transferred to completely new, much larger complexes and still achieve accuracy within 0.5 kcal mol − 1 . Using a principal component analysis and symmetry-adapted perturbation theory, we further show how the model can be used to predict the physical nature of a halogen bond, providing an efficient way to gain insight into the behavior of halogen-bonded systems. This means that the model can be used to highlight cases where induction or dispersion significantly affect the underlying nature of the interaction. Full article
(This article belongs to the Special Issue Halogen Bonding: Fundamentals and Applications)
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Review

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63 pages, 14258 KiB  
Review
Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood
by Pradeep R. Varadwaj, Arpita Varadwaj and Helder M. Marques
Inorganics 2019, 7(3), 40; https://doi.org/10.3390/inorganics7030040 - 12 Mar 2019
Cited by 122 | Viewed by 9312
Abstract
In addition to the underlying basic concepts and early recognition of halogen bonding, this paper reviews the conflicting views that consistently appear in the area of noncovalent interactions and the ability of covalently bonded halogen atoms in molecules to participate in noncovalent interactions [...] Read more.
In addition to the underlying basic concepts and early recognition of halogen bonding, this paper reviews the conflicting views that consistently appear in the area of noncovalent interactions and the ability of covalently bonded halogen atoms in molecules to participate in noncovalent interactions that contribute to packing in the solid-state. It may be relatively straightforward to identify Type-II halogen bonding between atoms using the conceptual framework of σ-hole theory, especially when the interaction is linear and is formed between the axial positive region (σ-hole) on the halogen in one monomer and a negative site on a second interacting monomer. A σ-hole is an electron density deficient region on the halogen atom X opposite to the R–X covalent bond, where R is the remainder part of the molecule. However, it is not trivial to do so when secondary interactions are involved as the directionality of the interaction is significantly affected. We show, by providing some specific examples, that halogen bonds do not always follow the strict Type-II topology, and the occurrence of Type-I and -III halogen-centered contacts in crystals is very difficult to predict. In many instances, Type-I halogen-centered contacts appear simultaneously with Type-II halogen bonds. We employed the Independent Gradient Model, a recently proposed electron density approach for probing strong and weak interactions in molecular domains, to show that this is a very useful tool in unraveling the chemistry of halogen-assisted noncovalent interactions, especially in the weak bonding regime. Wherever possible, we have attempted to connect some of these results with those reported previously. Though useful for studying interactions of reasonable strength, IUPAC’s proposed “less than the sum of the van der Waals radii” criterion should not always be assumed as a necessary and sufficient feature to reveal weakly bound interactions, since in many crystals the attractive interaction happens to occur between the midpoint of a bond, or the junction region, and a positive or negative site. Full article
(This article belongs to the Special Issue Halogen Bonding: Fundamentals and Applications)
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