On the directionality of halogen bonding

Huber, Stefan M.; Scanlon, Joseph D.; Jimenez−Izal, Elisa; Ugalde, Jesus M.; Infante, Ivan

doi:10.1039/c3cp50892g

Cited by 141 publications

(136 citation statements)

References 66 publications

Supporting

Mentioning

128

Contrasting

Unclassified

Order By: Relevance

“…While it had been an element of conventional wisdom for some time that the weakening of the HB associated with its bending arises from a reduction in electrostatic attraction between the two subunits, recent work [41][42][43][44][45] has laid the blame largely at the feet of exchange repulsion. The bending of the H-bond acts in some cases to destabilize the electrostatic attraction, and in others to have the opposite effect wherein Coulombic forces favor a bent structure.…”

Section: Energy Componentsmentioning

confidence: 98%

Angular dependence of hydrogen bond energy in neutral and charged systems containing CH and NH proton donors

Nepal

Scheiner

2015

Chemical Physics Letters

View full text Add to dashboard Cite

Section: Energy Componentsmentioning

confidence: 98%

Angular dependence of hydrogen bond energy in neutral and charged systems containing CH and NH proton donors

Nepal

Scheiner

2015

Chemical Physics Letters

View full text Add to dashboard Cite

“…4 Long before the term "halogen bond" came into general use, an overview on crystallographic studies revealing this kind of interaction was presented in the Nobel Lecture of O. Hassel. 11 A significant contribution of CT interactions was also concluded from the observation that the halogen-bonded I 2tetramethylthiourea complex is remarkably insensitive to the nature of diverse solvents, including protic-polar alcohols. 6 Subsequently a number of theoretical studies have been devoted to the analysis of the physical nature of halogen bonding and related σ-hole interactions.…”

Section: Introductionmentioning

confidence: 96%

The iodine–oxygen halogen bond: solid-state structures of 3-iodopropiolamides

et al. 2015

View full text Add to dashboard Cite

The solid-state structures of six 3-iodopropiolamides (I-CC-CO-NR 2 ; NR 2 = pyrrolidino, 2,5-dihydro-1Hpyrrolo, piperidino, morpholino, methylamino, amino) have been determined by XRD analysis. All but the parent 3-iodopropiolamide exhibit very short intermolecular iodine-oxygen contacts Ĳ2.754Ĳ2)-2.858Ĳ5) Å) leading to one-dimensional polymeric chains in the solid state. The shape of these chains and the packing arrangement depend on the size and ring conformation in the cases of cyclic tertiary amides (NR 2 ). In the structure of 3-iodopropiol-N-methylamide, I⋯O halogen bonds and N-H⋯O hydrogen bonds generate a two-dimensional, non-planar infinite network, while the crystal structure of 3-iodopropiolamide acetonitrile solvate is determined by a network of hydrogen bonds involving the CONH 2 moiety; the iodine atom, on the other hand, is coordinated to an acetonitrile molecule through a short I⋯N contact. CrystEngCommThis journal is

show abstract

“…The magnitude of the σ-hole is strictly related to the strength of the electrostatic interaction energy, even if this component alone is not able to explain all the characteristics of XBs. [29][30][31][32][33] Therefore, the proper understanding and description of σhole are of primary importance to model XB. The polar flattening is related to the "effective" shape of the halogen atom in the molecular entity and its contribution is expected to affect mainly the anisotropy of size repulsion term of the interaction.…”

Section: Introductionmentioning

confidence: 99%

Catching the role of anisotropic electronic distribution and charge transfer in halogen bonded complexes of noble gases

Bartocci

Belpassi

Cappelletti

et al. 2015

The Journal of Chemical Physics

View full text Add to dashboard Cite

The systems studied in this work are gas-phase weakly bound adducts of the noble-gas (Ng) atoms with CCl4 and CF4. Their investigation was motivated by the widespread current interest for the intermolecular halogen bonding (XB), a structural motif recognized to play a role in fields ranging from elementary processes to biochemistry. The simulation of the static and dynamic behaviors of complex systems featuring XB requires the formulation of reliable and accurate model potentials, whose development relies on the detailed characterization of strength and nature of the interactions occurring in simple exemplary halogenated systems. We thus selected the prototypical Ng-CCl4 and Ng-CF4 and performed high-resolution molecular beam scattering experiments to measure the absolute scale of their intermolecular potentials, with high sensitivity. In general, we expected to probe typical van der Waals interactions, consisting of a combination of size (exchange) repulsion with dispersion/induction attraction. For the He/Ne-CF4, the analysis of the glory quantum interference pattern, observable in the velocity dependence of the integral cross section, confirmed indeed this expectation. On the other hand, for the He/Ne/Ar-CCl4, the scattering data unravelled much deeper potential wells, particularly for certain configurations of the interacting partners. The experimental data can be properly reproduced only including a shifting of the repulsive wall at shorter distances, accompanied by an increased role of the dispersion attraction, and an additional short-range stabilization component. To put these findings on a firmer ground, we performed, for selected geometries of the interacting complexes, accurate theoretical calculations aimed to evaluate the intermolecular interaction and the effects of the complex formation on the electron charge density of the constituting moieties. It was thus ascertained that the adjustments of the potential suggested by the analysis of the experiments actually reflect two chemically meaningful contributions, namely, a stabilizing interaction arising from the anisotropy of the charge distribution around the Cl atom in CCl4 and a stereospecific electron transfer that occurs at the intermolecular distances mainly probed by the experiments. Our model calculations suggest that the largest effect is for the vertex geometry of CCl4 while other geometries appear to play a minor to negligible role.

show abstract

On the directionality of halogen bonding

Cited by 141 publications

References 66 publications

Angular dependence of hydrogen bond energy in neutral and charged systems containing CH and NH proton donors

Angular dependence of hydrogen bond energy in neutral and charged systems containing CH and NH proton donors

The iodine–oxygen halogen bond: solid-state structures of 3-iodopropiolamides

Catching the role of anisotropic electronic distribution and charge transfer in halogen bonded complexes of noble gases

Contact Info

Product

Resources

About