Improved General Understanding of the Hydrogen‐Bonding Phenomena: A Reply

Weinhold, Frank; Klein, Roger A.

doi:10.1002/anie.201500262

Cited by 44 publications

(24 citation statements)

References 38 publications

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“…The measured and calculated IR redshifts of the cationic and propanol clusters are nearly similar. This finding strongly supports the covalent character of H‐bonding and the concept of “anti‐electrostatic hydrogen bonds” (AEHB) as controversially discussed recently . There is also some indication that the formation of these clusters allows to supercool the IL and prevent it from crystallization.…”

Section: Figuresupporting

confidence: 83%

Spectroscopic Evidence for Clusters of Like‐Charged Ions in Ionic Liquids Stabilized by Cooperative Hydrogen Bonding

et al. 2016

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Direct spectroscopic evidence for hydrogen‐bonded clusters of like‐charged ions is reported for ionic liquids. The measured infrared O−H vibrational bands of the hydroxyethyl groups in the cations can be assigned to the dispersion‐corrected DFT calculated frequencies of linear and cyclic clusters. Compensating the like‐charge Coulomb repulsion, these cationic clusters can range up to cyclic tetramers resembling molecular clusters of water and alcohols. These ionic clusters are mainly present at low temperature and show strong cooperative effects in hydrogen bonding. DFT‐D3 calculations of the pure multiply charged clusters suggest that the attractive hydrogen bonds can compete with repulsive Coulomb forces.

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Section: Figuresupporting

confidence: 83%

Spectroscopic Evidence for Clusters of Like‐Charged Ions in Ionic Liquids Stabilized by Cooperative Hydrogen Bonding

et al. 2016

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“…Moreover, the considerable covalent nature of “AEHB” was ascribed to a strong n D →σ* H‐A CT interaction, based on natural bond orbital (NBO) analysis . This novel proposal of AEHB instantly stimulated heated discussions . The exemplary [F – ···HCO 3 ] 2– dianion was re‐examined by Frenking and Caramori, who proved the Coulombic force as the secondary significant stabilizing factor, despite the dominating orbital interaction .…”

Section: Introductionmentioning

confidence: 99%

“…[32,33] This novel proposal of AEHB instantly stimulated heated discussions. [34,35] The exemplary [F -ÁÁÁHCO 3 ] 2dianion was re-examined by Frenking and Caramori, who proved the Coulombic force as the secondary significant stabilizing factor, despite the dominating orbital interaction. [34] Since any unusual and controversial idea is also beguiling, we were prompted to carry out a more detailed investigation of the compatibility of AEHB with the conventional theory on H-bonding and furthermore on halogen bonding (X-bonding).…”

Section: Introductionmentioning

confidence: 99%

Hydrogen‐ and Halogen‐Bonds between Ions of like Charges: Are They Anti‐Electrostatic in Nature?

Wang

Zhang

et al. 2017

J Comput Chem

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Recent theoretical studies suggested that hydrogen bonds between ions of like charges are of a covalent nature due to the dominating n →σ* charge-transfer (CT) interaction. In this work, energy profiles of typical hydrogen (H) and halogen (X) bonding systems formed from ions of like charges are explored using the block-localized wavefunction (BLW) method, which can derive optimal geometries and wave functions with the CT interaction "turned off." The results demonstrate that the kinetic stability, albeit reduced, is maintained for most investigated systems even after the intermolecular CT interaction is quenched. Further energy decomposition analyses based on the BLW method reveal that, despite a net repulsive Coulomb repulsion, a stabilizing component exists due to the polarization effect that plays significant role in the kinetic stability of all systems. Moreover, the fingerprints of the augmented electrostatic interaction due to polarization are apparent in the variation patterns of the electron density. All in all, much like in standard H- and X-bonds, the stability of such bonds between ions of like charges is governed by the competition between the stabilizing electrostatic and charge transfer interactions and the destabilizing deformation energy and Pauli exchange repulsion. While in most cases of "anti-electrostatic" bonds the CT interaction is of a secondary importance, we also find cases where CT is decisive. As such, this work validates the existence of anti-electrostatic H- and X-bonds. © 2017 Wiley Periodicals, Inc.

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“…In this case, Coulomb repulsion of the anions can be compensated by hydrogen-bonding interactions, allowing protonated anions to form dimers or larger aggregates in which every individual component is negatively charged. While there recently has been controversy in the literature about the exact nature of the underlying interactions, 5 such aggregates are generally believed to be stabilised by attractive electrostatic interactions in the hydrogen bond that balance electrostatic repulsion. 6 …”

Section: Introductionmentioning

confidence: 99%

Efficient stabilisation of a dihydrogenphosphate tetramer and a dihydrogenpyrophosphate dimer by a cyclic pseudopeptide containing 1,4-disubstituted 1,2,3-triazole moieties

et al. 2017

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Improved General Understanding of the Hydrogen‐Bonding Phenomena: A Reply

Abstract: chemical bonds · electrostatic interactions · hydrogen-bonded complexes · hydrogen bonds · quantum-chemical calculations

Cited by 44 publications

References 38 publications

Spectroscopic Evidence for Clusters of Like‐Charged Ions in Ionic Liquids Stabilized by Cooperative Hydrogen Bonding

Spectroscopic Evidence for Clusters of Like‐Charged Ions in Ionic Liquids Stabilized by Cooperative Hydrogen Bonding

Hydrogen‐ and Halogen‐Bonds between Ions of like Charges: Are They Anti‐Electrostatic in Nature?

Efficient stabilisation of a dihydrogenphosphate tetramer and a dihydrogenpyrophosphate dimer by a cyclic pseudopeptide containing 1,4-disubstituted 1,2,3-triazole moieties

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