Halogen bond tunability II: the varying roles of electrostatic and dispersion contributions to attraction in halogen bonds

Riley, Kevin E.; Murray, Jane S.; Fanfrlík, Jindřich; Řezáč, Jan; Solá, Ricardo J.; Concha, Monica C.; Ramos, Felix M.; Politzer, Peter

doi:10.1007/s00894-012-1428-x

Cited by 190 publications

(154 citation statements)

References 52 publications

Supporting

Mentioning

147

Contrasting

Unclassified

Order By: Relevance

“…2 and especially in Fig. 7, and can also be seen in earlier reports [27,28,33,81]. They help to explain why hydrogen bonds tend overall to be less directional than other σ-hole interactions [33,96,97].…”

Section: Hydrogen Bondingsupporting

confidence: 55%

“…Dispersion is commonly considered to be associated with electronic correlation [79][80][81], i.e., the instantaneous correlated movements of the electrons in response to their mutual Coulombic repulsions. These movements create temporary dipoles which interact attractively, accounting for the stabilizing contribution of dispersion.…”

Section: The Nature Of σ-Hole Interactionsmentioning

confidence: 99%

See 1 more Smart Citation

σ-Hole Bonding: A Physical Interpretation

Politzer

Murray

Clark

2014

Topics in Current Chemistry

Self Cite

150

117

View full text Add to dashboard Cite

The anisotropic electronic densities of covalently-bonded Group IV-VII atoms frequently give rise to regions of positive electrostatic potential on the extensions of covalent bonds to these atoms. Through such positive "σ-holes," the atoms can interact attractively and highly directionally with negative sites such as the lone pairs of Lewis bases, anions, π electrons, etc. In the case of Group VII this is called "halogen bonding." Hydrogen bonding can be viewed as a less directional subset of σ-hole interactions. Since positive σ-holes often exist in conjunction with regions of negative potential, the atoms can also interact favorably with positive sites. In accordance with the Hellmann-Feynman theorem, all of these interactions are purely Coulombic in nature (which encompasses polarization and dispersion). The strength of σ-hole bonding increases with the magnitudes of the potentials of the positive σ-hole and the negative site; their polarizabilities must sometimes also be taken explicitly into account.

show abstract

Section: Hydrogen Bondingsupporting

confidence: 55%

Section: The Nature Of σ-Hole Interactionsmentioning

confidence: 99%

σ-Hole Bonding: A Physical Interpretation

Politzer

Murray

Clark

2014

Topics in Current Chemistry

Self Cite

150

117

View full text Add to dashboard Cite

show abstract

“…The relative magnitudes of these terms are highly dependent upon the identity of the halogen X, with the relative contribution of the electrostatic term increasing for larger X [27]. Recently, Riley et al [32] indicated that halogens with larger, more positive σ-holes tend to exhibit weaker dispersion interactions, which are attributable to the lower local polarizabilities of the larger σ-holes.…”

Section: Introductionmentioning

confidence: 97%

Cooperativity between fluorine-centered halogen bonds: investigation of substituent effects

et al. 2013

View full text Add to dashboard Cite

This article analyzes the substitution effects on cooperativity between fluorin-centered halogen bonds in NCF · · · NCF · · · NCX and CNF · · · CNF · · · CNX complexes, where X = H, F, Cl, CN, OH, and NH₂. These effects are investigated theoretically in terms of geometric and energetic features of the complexes, which are computed by ab initio methods. The topological analysis, based on the quantum theory of atoms in molecules (QTAIM), is used to characterize the interactions and analyze their enhancement with varying electron density at bond critical points. It is found that the complexes with electron-donating groups exhibit a strong cooperativity, while a much weaker cooperativity occurs in the NCF · · · NCF · · · NCCN and CNF · · · CNF · · · CNCN trimers. An excellent correlation is found between the cooperative energy in the ternary complexes and the calculated three-body interaction energies. The energy decomposition analysis (EDA) indicates that the electrostatic and dispersion effects play a main role in the cooperativity of fluorine-centered halogen bonding.

show abstract

“…Many reviews have described halogen bonding in detail, which is the best-known s-hole interaction. [6,[19][20][21][22] More recently, s-hole complexes with atoms of group IV, the tetrel (Tr) atoms, have been described, [24][25][26][27][28][29] and mostly focus on the heavier Tr atoms as tetrel-bond donors, leaving noncovalent carbon bonding much less studied. [30][31][32] In an sp 3 -hybridized electron-deficient C atom, there is only limited space available for an electron-rich guest molecule to nest itself.…”

mentioning

confidence: 99%

Nature of Noncovalent Carbon‐Bonding Interactions Derived from Experimental Charge‐Density Analysis

2015

View full text Add to dashboard Cite

In an effort to better understand the nature of noncovalent carbon-bonding interactions, we undertook accurate high-res-olution X-ray diffraction analysis of single crystals of 1,1,2,2-tetracyanocyclopropane. We selected this compound to study the fundamental characteristics of carbon-bonding interactions, because it provides accessible s holes. The study required extremely accurate experimental diffraction data, because the in-teraction of interest is weak. The electron-density distribution around the carbon nuclei, as shown by the experimental maps of the electrophilic bowl defined by a (CN)2C-C(CN)2 unit, was assigned as the origin of the interaction. This fact was also evidenced by plotting the D21(r) distribution. Taken together, the obtained results clearly indicate that noncovalent carbon bonding can be explained as an interaction between confront-ed oppositely polarized regions. The interaction is, thus elec-trophilic-nucleophilic (electrostatic) in nature and unambigu-ously considered as attractive.Attractive intermolecular electrostatic interactions encompass electron-rich and electron-poor regions of two molecules that complement each other.[1] Electron-rich entities are typically anions or lone-pair electrons and the most well-known elec-tron-poor entity is the hydrogen atom. Consequently, hydro-gen bonding is undoubtedly the most exploited supramolec-ular interaction.[2] Nowadays, another common electron-poor entity is attracting increasing attention in the literature. It is the 's hole', which can be defined as an electron-deficient anti-bonding orbital of a covalent bond. [3-13] Such regions of posi-tive electrostatic potential have been largely studied for atoms of groups V, VI, and VII (pnicogen, [14,15] chalcogen, [16][17][18] and hal-ogen [19-22] bonding, respectively [23] ) . Many reviews have described halogen bonding in detail, which is the best-known s-hole interaction. [6,[19][20][21][22] More recently, s-hole complexes with atoms of group IV, the tetrel (Tr) atoms, have been described, [24][25][26][27][28][29] and mostly focus on the heavier Tr atoms as tetrel-bond donors, leaving noncovalent carbon bonding much less studied. [30][31][32] In an sp 3 -hybridized electron-deficient C atom, there is only limited space available for an electron-rich guest molecule to nest itself. [31,32] To exem-plify this, we have represented in Figure 1 (right) the MEP sur- Figure 1.face of 1,1,2,2-tetracyanoethane (staggered conformation). The s hole is small and it is surrounded by negative belts, which hinder interactions with any concentration of negative charge (lone pair or anion). However, if the MEP surface is computed in the eclipsed conformation (C2v), the resulting s hole is more exposed and the electrostatic potential is considerable more positive. As a matter of fact, it has been recently demonstrated that the (CN) 2 C-C(CN) 2 motif of 1,1,2,2-tetracyanocyclopropane is an excellent carbon-bond donor, because the s hole is very exposed.[33] Moreover, it is synthetically accessible and the N_ C...

show abstract

Halogen bond tunability II: the varying roles of electrostatic and dispersion contributions to attraction in halogen bonds

Cited by 190 publications

References 52 publications

σ-Hole Bonding: A Physical Interpretation

σ-Hole Bonding: A Physical Interpretation

Cooperativity between fluorine-centered halogen bonds: investigation of substituent effects

Nature of Noncovalent Carbon‐Bonding Interactions Derived from Experimental Charge‐Density Analysis

Contact Info

Product

Resources

About