Intramolecular halogen bonding: an interacting quantum atoms study

Yahia-Ouahmed, Meziane; Tognetti, Vincent; Joubert, Laurent

doi:10.1007/s00214-015-1796-2

Cited by 17 publications

(13 citation statements)

References 110 publications

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“…Riley et al suggested that the C-Br• • • Cl angles for some halogen bonded complexes with cationic halogen bond donors the secondary interaction that occurs between Cl − and the cation ammonium group (angles greater than~120 • ) enhances exchange repulsion associated with the halogen's oblate shape, which is probably chiefly responsible for halogen bond directionality, as has been found for neutral halogen bonds [203]. Others argued that the contribution due to electrostatics may be significant in some complexes, as significant as dispersion and exchange in the others, but the equilibrium geometry of a complex system that is stabilized by a noncovalent interaction (no matter what type of bond it is) is always driven by all of them [12,45,47,49,51,52,204]. This suggests that the directionality of the interaction is simply a representation of the delicate balance between all component interactions acting on the nuclei of atoms.…”

Section: Is the Directionality Feature In Halogen-centered Noncovalenmentioning

confidence: 94%

Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood

2019

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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.

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Section: Is the Directionality Feature In Halogen-centered Noncovalenmentioning

confidence: 94%

Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood

2019

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“…QTAIM and IQA have helped decipher the nature of halogen 186,[196][197][198] and hydrogen 168,[199][200][201][202] bonds, but discussion on their use within the context of London dispersion interactions is still ongoing. 203 Even if QTAIM can be used for visualizing van der Waals interactions, interpreting the results is by no means "black-box."…”

Section: Applicability and Usefulness Of Visualization Toolsmentioning

confidence: 99%

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Pastorczak¹,

Corminbœuf²

2017

The Journal of Chemical Physics

105

102

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Today's quantum chemistry methods are extremely powerful but rely upon complex quantities such as the massively multidimensional wavefunction or even the simpler electron density. Consequently, chemical insight and a chemist's intuition are often lost in this complexity leaving the results obtained difficult to rationalize. To handle this overabundance of information, computational chemists have developed tools and methodologies that assist in composing a more intuitive picture that permits better understanding of the intricacies of chemical behavior. In particular, the fundamental comprehension of phenomena governed by non-covalent interactions is not easily achieved in terms of either the total wavefunction or the total electron density, but can be accomplished using more informative quantities. This perspective provides an overview of these tools and methods that have been specifically developed or used to analyze, identify, quantify, and visualize non-covalent interactions. These include the quantitative energy decomposition analysis schemes and the more qualitative class of approaches such as the Non-covalent Interaction index, the Density Overlap Region Indicator, or quantum theory of atoms in molecules. Aside from the enhanced knowledge gained from these schemes, their strengths, limitations, as well as a roadmap for expanding their capabilities are emphasized. ©2017Author(s

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“…Actually, other species including radicals [ 9 ], metal hydrides [ 10 , 11 ], carbenes [ 12 , 13 ] are also taken as the electron donors in XBs. Furthermore, intramolecular XBs were also found to play a key role in structural chemistry [ 14 , 15 ].…”

Section: Introductionmentioning

confidence: 99%

Multicenter (FX)n/NH3 Halogen Bonds (X = Cl, Br and n = 1–5). QTAIM Descriptors of the Strength of the X∙∙∙N Interaction

et al. 2017

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In the present work an in depth deep electronic study of multicenter XBs (FX)n/NH3 (X = Cl, Br and n = 1–5) is conducted. The ways in which X∙∙∙X lateral contacts affect the electrostatic or covalent nature of the X∙∙∙N interactions are explored at the CCSD(T)/aug-cc-pVTZ level and in the framework of the quantum theory of atoms in molecules (QTAIM). Calculations show that relatively strong XBs have been found with interaction energies lying between −41 and −90 kJ mol−1 for chlorine complexes, and between −56 and −113 kJ mol−1 for bromine complexes. QTAIM parameters reveal that in these complexes: (i) local (kinetics and potential) energy densities measure the ability that the system has to concentrate electron charge density at the intermolecular X∙∙∙N region; (ii) the delocalization indices [δ(A,B)] and the exchange contribution [VEX(X,N)] of the interacting quantum atoms (IQA) scheme, could constitute a quantitative measure of the covalence of these molecular interactions; (iii) both classical electrostatic and quantum exchange show high values, indicating that strong ionic and covalent contributions are not mutually exclusive.

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Intramolecular halogen bonding: an interacting quantum atoms study

Cited by 17 publications

References 110 publications

Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood

Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Multicenter (FX)n/NH3 Halogen Bonds (X = Cl, Br and n = 1–5). QTAIM Descriptors of the Strength of the X∙∙∙N Interaction

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