Competitive Halide Binding by Halogen Versus Hydrogen Bonding: Bis‐triazole Pyridinium

Nepal, Binod; Scheiner, Steve

doi:10.1002/chem.201501921

Cited by 33 publications

(32 citation statements)

References 71 publications

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“…[68,69] This basis set and functional have been applied previously to similar sorts of systems to good effect. [14,[33][34][35][70][71][72][73][74][75] Relativistic effects are expected to be most significant for atoms below the third row of the periodic table. Minima on each potential energy surface were assured by the absence of any negative frequencies.…”

Section: Methodsmentioning

confidence: 99%

“…[28] Chudzinski et al [29] obtained quantitativee stimates of the contribution of halogen bonding to the binding of anions to bipodal receptors, along with notingapreferencef or halides over oxoanions. [32] Our own group has engaged in severalr ecent studies in this arena,w here our quantum calculations have compared halogen with hydrogen-bonded receptors.R eplacemento ft he Hbondingp rotons of bis-triazole-pyridine by halogen atoms [33] demonstratedt hat Is ubstitution yields the greatest binding enhancementw ith various halides. Halogen bonding exertss electivity for bromide over chloride, or othera nions in as et of tripodalr eceptors.…”

Section: Introductionmentioning

confidence: 99%

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Highly Selective Halide Receptors Based on Chalcogen, Pnicogen, and Tetrel Bonds

Scheiner

2016

Chemistry A European J

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101

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The interactions of halides with a number of bipodal receptors were examined by quantum chemical methods. The receptors were based on a dithieno thiophene framework in which two S atoms can engage in a pair of chalcogen bonds with a halide. These two S atoms were replaced by P and As atoms to compare chalcogen with pnicogen bonding, and by Ge which engages in tetrel bonds with the receptor. Zero, one, and two O atoms were added to the thiophene S atom which is not directly involved in the interaction with the halides. Fluoride bound the most strongly, followed by Cl , Br , and I , respectively. Replacing S by the pnicogen bonds of P strengthened the binding, as did moving down to As in the third row of the periodic table. A further large increment is associated with the switch to the tetrel bonds of Ge. Even though the thiophene S atom is remote from the binding site, each additional O atom added to it raises the binding energy, which can be quite large, as much as 63 kcal mol for the Ge⋅⋅⋅F interaction. The receptors have a pronounced selectivity for F over the other halides, as high as 27 orders of magnitude. The data suggest that incorporation of tetrel atoms may lead to new and more powerful halide receptors.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Highly Selective Halide Receptors Based on Chalcogen, Pnicogen, and Tetrel Bonds

Scheiner

2016

Chemistry A European J

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101

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“…Previous calculations on related ion-pair XBs often employ the M06-2X functional, [34][35][36][37]56] which performsw ell for traditional (i.e.,n on-ion-pair) XBs [57] and interactions involving anionic electron donors. [58] On the other hand, B3LYP is undoubtedly one of the most popularf unctionals and has been used in several theoretical studies, [55,59] including ion-pair XBs.…”

Section: Computational Detailsmentioning

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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“…All these interactions have recentlyb een widely explored in the fields of crystallography, [26] supramolecular chemistry, [27,28] biochemistry, [29,30] and catalysis, [31][32][33] just to name af ew.H owever,w ew ere particularly interested in another field, hole interactions as receptors [34] of halides. [35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52][53][54] In ar ecent article, Scheiner [55] proposedadithieno-thiophenef ramework (1 Y ,s ee Figure 1) to create selectiveh alide receptors. By replacing the upper sulfur atoms with germanium atoms, strong s holes and correspondinglys trong tetrel bonds are formed with halides.…”

Section: S-hole Interactionsmentioning

confidence: 99%

Ping‐Pong Tunneling Reactions: Can Fluoride Jump at Absolute Zero?

Nandi

Sucher

Kozuch

2018

Chemistry A European J

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In a recent study, Scheiner designed a double-germanium-based fluoride receptor that binds the halogen by means of strong tetrel bonds (Chem. Eur. J. 2016, 22, 18850). In this system the F binds to the germanium atoms in an asymmetric fashion, thereby producing a double-well potential in which the fluoride can jump from one germanium to the other as in a ping-pong game. Herein we prove through the use of computational tools that at cryogenic temperatures this rearrangement occurs by heavy-atom quantum mechanical tunneling. The inductive strength of the substituents and the polarity of the solvent can modify the barrier and the tunneling rate. But the strongest effect is observed upon modification of the geometry of the molecule by specific substitutions that affect the barrier width, the most critical factor in a tunneling mechanism. We postulate two experimental tests, one by microwave spectroscopy and one by cryogenic NMR spectroscopy, that can prove the predicted fluoride tunneling.

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Competitive Halide Binding by Halogen Versus Hydrogen Bonding: Bis‐triazole Pyridinium

Cited by 33 publications

References 71 publications

Highly Selective Halide Receptors Based on Chalcogen, Pnicogen, and Tetrel Bonds

Highly Selective Halide Receptors Based on Chalcogen, Pnicogen, and Tetrel Bonds

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

Ping‐Pong Tunneling Reactions: Can Fluoride Jump at Absolute Zero?

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