Polarized IR spectra of resonance assisted hydrogen bond (RAHB) in 2-hydroxyazobenzenes

Роспенк, М.; Majewska, Paulina; Czarnik-Matusewicz, Bogusława; Sobczyk, L.

doi:10.1016/j.chemphys.2006.03.013

Cited by 12 publications

(12 citation statements)

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“…Since the proposal of the intramolecular resonance-assisted hydrogen bond (RAHB) concept, 1−6 extensive studies have been conducted both experimentally 7,8 and computationally, 9−14 in attempts to understand and utilize the RAHB phenomenon, where the intramolecular H bond is strengthened with the shortening of bond, decreasing of the O−H vibrational frequency, and abnormal downfield 1 H NMR chemical shift. RAHB highlights the interplay between resonance and hydrogen bonding and has been found to be crucial in protein folding and DNA pairing.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Since the proposal of the intramolecular resonance-assisted hydrogen bond (RAHB) concept, − extensive studies have been conducted both experimentally , and computationally, − in attempts to understand and utilize the RAHB phenomenon, where the intramolecular H bond is strengthened with the shortening of bond, decreasing of the O–H vibrational frequency, and abnormal downfield 1 H NMR chemical shift. RAHB highlights the interplay between resonance and hydrogen bonding and has been found to be crucial in protein folding and DNA pairing. − Yet there are controversies over the nature of RAHB, as there is a possibility that the stronger intramolecular RAHB in unsaturated compounds than in their saturated analogues does not necessarily means that there is a RAHB phenomenon; rather, it may simply result from the constraints imposed by the σ-skeleton framework. − But it may be inappropriate to compare a conjugated system with its saturated analogue, as they have quite different σ-skeleton frameworks.…”

Section: Introductionmentioning

confidence: 99%

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The Origin of the Non-Additivity in Resonance-Assisted Hydrogen Bond Systems

et al. 2017

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The concept of resonance-assisted hydrogen bond (RAHB) has been widely accepted, and its impact on structures and energetics can be best studied computationally using the block-localized wave function (BLW) method, which is a variant of ab initio valence bond (VB) theory and able to derive strictly electron-localized structures self-consistently. In this work, we use the BLW method to examine a few molecules that result from the merging of two malonaldehyde molecules. As each of these molecules contains two hydrogen bonds, these intramolecular hydrogen bonds may be cooperative or anticooperative, depended on their relative orientations, and compared with the hydrogen bond in malonaldehyde. Apart from quantitatively confirming the concept of RAHB, the comparison of the computations with and without π resonance shows that both σ-framework and π-resonance contribute to the nonadditivity in these RAHB systems with multiple hydrogen bonds.

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The Origin of the Non-Additivity in Resonance-Assisted Hydrogen Bond Systems

et al. 2017

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“…Gilli et al [14][15][16] proposed the concept of RAHBs, this has had great success in many fields such as organic chemistry, [17][18][19][20][21] infrared spectroscopy, 22 nuclear magnetic resonance, 23 electron diffraction, 24 or biological chemistry. [25][26][27][28] The proton donor and proton acceptor groups in RAHBs are connected through a chain of p-conjugated double bonds, and the standard explanation of the noticeable strength of these interactions is based on a chemically intuitive reasoning in which the conjugated bonds display an equalization of lengths through a pseudo-ring.…”

Section: Introductionmentioning

confidence: 99%

The nature of resonance-assisted hydrogen bonds: a quantum chemical topology perspective

Guevara‐Vela

Romero-Montalvo

Costales

et al. 2016

Phys. Chem. Chem. Phys.

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Title: The nature of resonance-assisted hydrogen bonds: a quantum chemical topology perspectiveThis work addresses the nature of Resonance Assisted Hydrogen Bonds (RAHBs) by considering malonaldehyde whose H-bonded (closed) and non H-bonded (open) conformations are represented in the bottom and top of the seesaws respectively. Although delocalization indices are more uniform in the closed form (seesaw in the left), the number of delocalized electrons diminish on RAHB formation. The interaction is characterized by an increase/decrease in the intra-atomic/inter-atomic exchange energies as schematized with sparks in the highlighted seesaw in the right. The artwork is due to Mr Víctor Duarte Alaniz. indicate that the p-conjugated bonds allow for a larger adjustment of electron density throughout the H-bonded system as compared with non-conjugated carbonyl molecules. This rearrangement of charge distribution is a response to the electric field due to the H atom involved in the hydrogen bonding of the considered compounds. As opposed to the usual description of RAHB interactions, these HBs lead to a larger electron localisation in the system, and concomitantly to larger QTAIM charges which in turn lead to stronger electrostatic, polarization and charge transfer components of the interaction. Overall, the results presented here offer a new perspective on the cause of strengthening of these important interactions.

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“…[9] Figure 2 (a) shows this interaction between the hydrogen bond and the π system within malondialdehyde, CHO−CH − − CH−OH. Resonance assisted hydrogen bonds have been of considerable interest in physical chemistry, a situation which has lead to numerous theoretical [10][11][12] and experimental [13,14] reports concerned with the nature of these HBs. In addition, the RAHB concept has been used to better understand intermolecular interactions in relevan systems in chemistry and biology, like those present in DNA [15][16][17] and proteins [3] .…”

Section: Introductionmentioning

confidence: 99%