Understanding the magnitude and origin of bidentate charge-assisted halogen bonds of halo-perfluorocarbons and halo-hydrocarbons with halide anions

Shi, Qi; Lu, Yunxiang; Fan, Ji-Cai; Zou, Jian‐Wei; Wang, Yanhua

doi:10.1016/j.theochem.2007.11.037

Cited by 17 publications

(9 citation statements)

References 65 publications

(51 reference statements)

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“…Anions, particularly halides, participate readily as halogen‐bond acceptors in the solid state,7 including examples of crystalline networks in which a single anion accepts multiple halogen bonds 8. This last observation suggests that a multidentate halogen‐bond donor capable of donating several halogen bonds in a convergent fashion might be capable of anion binding in dilute solution 9…”

Section: Binding Constants Of 1 A–d With Nbu4n+x− (Acetone 295 K)mentioning

confidence: 95%

A Tridentate Halogen‐Bonding Receptor for Tight Binding of Halide Anions

et al. 2010

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Drei passend orientierte elektronenarme Iodarylgruppen bilden die Grundlage des ersten Anionenrezeptors (siehe Bild; weiß H, grau C, rot O, blau F, lila I, grün Cl), der ausschließlich Halogenbrücken verwendet, um eine hochaffine molekulare Erkennung in verdünnter Lösung zu erzielen. In seiner Anionenselektivität unterscheidet sich der Rezeptor von strukturverwandten Wasserstoffbrückenrezeptoren.

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Section: Binding Constants Of 1 A–d With Nbu4n+x− (Acetone 295 K)mentioning

confidence: 95%

A Tridentate Halogen‐Bonding Receptor for Tight Binding of Halide Anions

et al. 2010

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“…As we have just seen, the negative lateral sides of another covalently bonded halogen atom can play this role. The p electrons of unsaturated molecules-in arenes, [58,[77][78][79][80] alkenes, alkynes, [81,82] and so forthcan serve this purpose, as can anions, [83,84] hydrides, [85][86][87] and so forth. These are all simply examples of halogen bonding.…”

Section: Halogen-bonded Complexesmentioning

confidence: 99%

Halogen Bonding: An Interim Discussion

2013

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Halogen bonding is a noncovalent interaction that is receiving rapidly increasing attention because of its significance in biological systems and its importance in the design of new materials in a variety of areas, for example, electronics, nonlinear optical activity, and pharmaceuticals. The interactions can be understood in terms of electrostatics/polarization and dispersion; they involve a region of positive electrostatic potential on a covalently bonded halogen and a negative site, such as the lone pair of a Lewis base. The positive potential, labeled a σ hole, is on the extension of the covalent bond to the halogen, which accounts for the characteristic near-linearity of halogen bonding. In many instances, the lateral sides of the halogen have negative electrostatic potentials, allowing it to also interact favorably with positive sites. In this discussion, after looking at some of the experimental observations of halogen bonding, we address the origins of σ holes, the factors that govern the magnitudes of their electrostatic potentials, and the properties of the resulting complexes with negative sites. The relationship of halogen and hydrogen bonding is examined. We also point out that σ-hole interactions are not limited to halogens, but can also involve covalently bonded atoms of Groups IV-VI. Examples of applications in biological/medicinal chemistry and in crystal engineering are mentioned, taking note that halogen bonding can be "tuned" to fit various requirements, that is, strength of interaction, steric factors, and so forth.

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“…Very often theoretical studies on charge-assisted XBs deal with interactions between neutral halogenatedm olecules and anions, for example, RÀBr···Br À ,R ÀBr···NC À , [25] or CR 3 X···Br À ···XCR 3 bidentate systems (R = F, H; X= Br,I ). [26] In some cases, such as in FCl···CNR complexes (R = CN, NC, NO 2 ,F , CF 3 ,C l, Br,H ,C CF,C CH, CH 3 ,S iH 3 ,L i, and Na), traditional halogen bonds are formed when CNR is aw eak base, but with strongb ases, such as CNLi and CNNa,i on-pair halogen bonds are formed. [27] As imilar effect was observed in related FCl···CNH···(CNR) n (R = H, Li, and Na), [28] Cl 2 ···CNR, Cl 2 ···SiNR, or FCl···SiNR [29] complexes.…”

Section: Introductionmentioning

confidence: 99%

“…Very often theoretical studies on charge‐assisted XBs deal with interactions between neutral halogenated molecules and anions, for example, R−Br⋅⋅⋅Br − , R−Br⋅⋅⋅NC − , or CR 3 X⋅⋅⋅Br − ⋅⋅⋅XCR 3 bidentate systems (R=F, H; X=Br, I) . In some cases, such as in FCl⋅⋅⋅CNR complexes (R=CN, NC, NO 2 , F, CF 3 , Cl, Br, H, CCF, CCH, CH 3 , SiH 3 , Li, and Na), traditional halogen bonds are formed when CNR is a weak base, but with strong bases, such as CNLi and CNNa, ion‐pair halogen bonds are formed .…”

Section: Introductionmentioning

confidence: 99%

Ion‐Pair Halogen Bonds in 2‐Halo‐Functionalized Imidazolium Chloride Receptors: Substituent and Solvent Effects

Nunes

Costa

2017

Chemistry An Asian Journal

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The interaction of 2-halo-functionalized imidazolium derivatives (n-X ; X=Cl, Br, I) with a chloride anion through ion-pair halogen bonds (n-X⋅Cl) was studied by means of DFT and ab initio calculations. A method benchmark was performed on 2-bromo-1H-imidazol-3-ium in association with chloride (1-Br⋅Cl); MP2 yielded the best results when compared with CCSD(T) calculations. The interaction energies (ΔE) in the gas phase are high and, although the electrostatic interaction is strong owing to the ion-pair nature of the system, large X⋅⋅⋅Cl Wiberg bond orders and contributions from charge transfer (nCl- →σ*C-X) are obtained. These values drop considerably in chloroform and water; this shows that solvent plays a role in modulating the interaction and that gas-phase calculations are particularly unrealistic for experimental applications. The introduction of electron-withdrawing groups in the 4,5-positions of the imidazolium (e.g., -NO , -F) increases the halogen-bond strength in both the gas phase and solvent, including water. The effect of the substituents on the 1,3-positions (N-H groups) also depends on the solvent. The variation of ΔE can be predicted through a two-parameter linear regression that optimizes the weights of charge-transfer and electrostatic interactions, which are different in vacuum and in solvent (chloroform and water). These results could be used in the rational design of efficient chloride receptors based on halogen bonds that work in solution, in particular, in an aqueous environment.

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Understanding the magnitude and origin of bidentate charge-assisted halogen bonds of halo-perfluorocarbons and halo-hydrocarbons with halide anions

Cited by 17 publications

References 65 publications

A Tridentate Halogen‐Bonding Receptor for Tight Binding of Halide Anions

A Tridentate Halogen‐Bonding Receptor for Tight Binding of Halide Anions

Halogen Bonding: An Interim Discussion

Ion‐Pair Halogen Bonds in 2‐Halo‐Functionalized Imidazolium Chloride Receptors: Substituent and Solvent Effects

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