Comment on “Analysis of CF···FC Interactions on Cyclohexane and Naphthalene Frameworks”

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

doi:10.1021/jp509101s

Cited by 15 publications

(8 citation statements)

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“…energetic and spectroscopic, and so forth. Commenting on the reliability of C−F···F−C interactions reported by Cormanich et al, a Tognetti et al have clarified that the knowledge of interactions may be useful for inferring the electron topology only by restricting to the exchange part of the energy, but not the interaction energy, and that the electron density topology cannot be univocally used to predict interatomic interactions. Similarly, Bartashevich et al and Varadwaj et al b have added that the treatment of the low RDG regions is very much vaguer especially in the vicinity of (3,+1) ring and (3,+3) cage critical points, as the NCI isosurfaces near the latter two cps are often produced to be unphysical compared to what are normally appeared at the (3,−1) bcps.…”

Section: Resultsmentioning

confidence: 99%

Hexahalogenated and their mixed benzene derivatives as prototypes for the understanding of halogen···halogen intramolecular interactions: New insights from combined DFT, QTAIM‐, and RDG‐based NCI analyses

Varadwaj

Jin

2015

J Comput Chem

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A large number of fully halogenated benzene derivatives containing the fluorine, chlorine, bromine, and iodine atoms have been experimentally synthesized both as single- and co-crystals (e.g., Desiraju et al., Chem. Eur. J. 2006, 12, 2222), yet the natures of the halogen ··· halogen interactions between the vicinal halogens in these compounds within the intramolecular domain are undisclosed. Given a fundamental understanding of these interactions is incredibly important in many areas of chemical, biological, supramolecular, and material sciences, we present here our newly discovered theoretical results that delineate whilst the nature of an F···F interaction in a pair of two adjacent fluorine atoms in either of the hexafluorobenzene and 1,4-dibromotetrafluorobenzene compounds examined is almost unclear, each of the latter three hexahalogenated benzene derivatives (viz., C6 Cl6 , C6 Br6 , and C6 I6 ), and each of the seven of their fully mixed hexahalogenated benzene analogues, are found to be stabilized by means of a number of halogen···halogen interactions, each a form of long-range attraction within the intramolecular domain. The Molecular Electrostatic Surface Potential model was found to be unsurprisingly unsuitable in unraveling any of the aforesaid attractions between the halogen atoms. However, such interactions successfully enunciated by a set of noncovalent interaction descriptors of geometrical, topological, and electrostatic origins. These latter properties were extracted combining the results of the Density Functional Theory electronic structure calculations with those revealed from Atoms in Molecules, and Reduced Density Gradient charge density-based topological calculations, and are expounded in detail to formalize the conclusions. © 2015 Wiley Periodicals, Inc.

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Section: Resultsmentioning

confidence: 99%

Hexahalogenated and their mixed benzene derivatives as prototypes for the understanding of halogen···halogen intramolecular interactions: New insights from combined DFT, QTAIM‐, and RDG‐based NCI analyses

Varadwaj

Jin

2015

J Comput Chem

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“…4 represents the variation of the electron density Laplacian in the Br…N line for the Cl 3 COBr…NH 3 complexes with Br…N = 2.91 Å. Let us also recall that, as a consequence of the Poincaré-Hopf theorem, a (3, −1) critical point [belonging to the interatomic surface (IAS)] will be created between the Cl 3 COX and NH 3 moieties when the interaction between them is switched on [46,47], at any interaction distance and independently of the interaction nature (destabilizing or not). As it is located almost exactly on the X…N line, we have thus an expedient way for separating any halogen and nitrogen basins along the X…N line [since this (3, −1) point belongs to the corresponding interatomic surface].…”

Section: Resultsmentioning

confidence: 99%

Electron density Laplacian and halogen bonds

Tognetti

Joubert

2015

Theor Chem Acc

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They have been characterized by a wide arsenal of experimental tools (almost all flavors of spectroscopies, see Ref. [7][8][9] for typical examples) as well as by multifarious theoretical approaches [10]: molecular orbitals analysis [11], energetic decompositions [12], conceptual DFT [13,14], Bader's atoms-in-molecules (QTAIM) theory [15][16][17][18], etc., each of them conveying complementary insight to unravel their physical nature. Among them, the σ-hole concept [19][20][21][22][23][24], forged and developed by Politzer and coworkers, has achieved a high popularity, owing to its simplicity, its versatility and its ubiquity (since it is also at work in other non-covalent bonds like pnicogen and carbon bonds), and it has clearly represented a considerable breakthrough for the understanding of these non-conventional interactions.Let us recall that the σ-hole is plainly defined as a region of positive molecular electrostatic potential (MEP) on the outer side of the halogen atom. This space region is thus prone to interact with the lone electron pair(s) carried by the partner. Recently, a similar analysis (also valid for homologous noncovalent bonds) has been proposed using, as the primary physical observable, the electron density Laplacian ∇ 2 ρ(� r) [25][26][27][28] instead of MEP, leading to the so-called lump-hole interaction paradigm [29]: the electron-deficient region at the periphery of the halogen atom is then viewed as a "hole" that can be filled by the electron-rich Lewis base's lump. Indeed, it is very well known that charge depletion areas are easily characterized by positive ∇ 2 ρ(� r) values, while charge concentration occurs when ∇ 2 ρ(� r) is negative.The aim of this paper is to provide formal evidence that the two descriptions (σ-hole point of view based on MEP, lump-hole viewpoint based on density Laplacian) are actually closely related and to hint how the latter can be used to evaluate interaction energies in the framework of Bader's atoms-in-molecules (QTAIM) [30,31] theory. Note Abstract In this paper, we discuss the physical meaning of the electron density Laplacian values in the valence region of halogen atoms and its relevance for the interpretation of halogen bonds formation. To this aim, formal relationships between Laplacian, electrostatic potential and molecular energies are derived, in particular within the framework of Bader's atoms-in-molecules theory. Simple one-dimensional models are finally provided to illustrate the semiquantitative usefulness of such tools.

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“…It should be noted that the F/F interactions are in a way controversial. 90,91 Bader analysis of the periodic electronic density followed by eqn (3) gives a possibility to reveal relative contributions of pstacking and inter-stacking interactions to the E latt energy. 62,84 The E latt computation in a two-component 1 : 1 crystal is carried out in two separate steps.…”

Section: Intermolecular Interactions In Considered Crystalsmentioning

confidence: 99%

Interplay of π-stacking and inter-stacking interactions in two-component crystals of neutral closed-shell aromatic compounds: periodic DFT study

et al. 2020

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Comment on “Analysis of CF···FC Interactions on Cyclohexane and Naphthalene Frameworks”

Cited by 15 publications

References 10 publications

Hexahalogenated and their mixed benzene derivatives as prototypes for the understanding of halogen···halogen intramolecular interactions: New insights from combined DFT, QTAIM‐, and RDG‐based NCI analyses

Hexahalogenated and their mixed benzene derivatives as prototypes for the understanding of halogen···halogen intramolecular interactions: New insights from combined DFT, QTAIM‐, and RDG‐based NCI analyses

Electron density Laplacian and halogen bonds

Interplay of π-stacking and inter-stacking interactions in two-component crystals of neutral closed-shell aromatic compounds: periodic DFT study

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