Lack of resonance assistance in a classical intramolecular hydrogen bond: An exploration from quantum theory of atoms‐in‐molecules perspective

Paul, Bijan Kumar

doi:10.1002/poc.3999

Cited by 6 publications

(1 citation statement)

References 54 publications

(189 reference statements)

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“…Many computational studies − and experimental works − can be found related to intramolecular and intermolecular RAHBs. The origin of the additional strength of RAHB as compared with conventional HBs is still a subject of an ongoing debate.…”

Section: Introductionmentioning

confidence: 99%

Tuning the Strength of the Resonance-Assisted Hydrogen Bond in Acenes and Phenacenes with Two o-Hydroxyaldehyde Groups—The Importance of Topology

et al. 2019

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The fact that intramolecular resonance-assisted hydrogen bonds (RAHBs) are stronger than conventional ones is attributed to the partial delocalization of the electrons within the hydrogen bond (HB) motif, the so-called quasi-ring. If an aromatic ring is involved in the formation of the RAHB, previous studies have shown that there is an interplay between aromaticity and HB strength. Moreover, in 1,3-dihydroxyaryl-2-aldehydes, some of us found that the position of the quasiring formed by the substituents interacting through RAHB influences the strength of the H-bonding, the HBs being stronger when a kinked-like structure is generated by formation of the quasi-ring. In this work, we explore this concept further by considering a set of acenes and phenacenes of different sizes with two ohydroxyaldehyde substituents. Calculations with the CAM-B3LYP/6-311+G(d,p)+GD3B method show that for long acenes or phenacenes, once the substituent effect loses importance because quasi-rings are pull apart far from each other, the different topologies rule the HB distances. This fact can be explained in most cases using an extended Clar's aromatic -sextet model. In some kinked systems, however, the justification from the Clar model has to be complemented by taking into account the repulsion between hydrogen atoms. Triphenylene-like compounds with different number of benzene rings have been studied finding out a very good relationship between aromaticity of the ipso-and quasi-rings with the RAHB distances. This result confirms the importance of the communication of the -systems of the ipso-and quasi-rings. Gilli et al. 6-9 attributed it to the delocalization of the -electrons. Mo et al, 16,18 provided further evidences that the enhanced HB comes from the charge flow from the HB donor to the acceptor through the -conjugation. Recently, Grosch et al. 11 arrived to the conclusion that  polarization and  charge transfer are the responsible for enhancing RAHB in line with the Gilli et al. proposal, although they emphasized that there is no resonance assistance in the sense of an interplay between σ charge transfer and π polarization. Moreover, other researchers, like Sanz et al., 25,26 argued that the characteristics of the -skeleton, and not the resonance assistance phenomenon, is the main responsible for the extra stability of RAHB. Also, Guevara-Vela et al. 13,14,24 analyzed the nature of the RAHB to conclude that there is an increase in electron localization of -electrons (not delocalization as expected from Gilli's interpretation) in the quasi-ring of RAHB. This localization leads to greater electrostatic, polarization, and charge transfer effects that result in stronger H-bonds. Thus, we can find different interpretations of the basis of the "assistance" in RAHBs. Scheme 2. The two main resonance structures involved in the resonance-assisted hydrogen bond in o-hydroxybenzaldehyde.

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Section: Introductionmentioning

confidence: 99%

Tuning the Strength of the Resonance-Assisted Hydrogen Bond in Acenes and Phenacenes with Two o-Hydroxyaldehyde Groups—The Importance of Topology

et al. 2019

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Blue‐ and Red‐Shifting C−H⋯O Hydrogen Bonds of Cyclic Ethers with Haloforms: Effect of Ring‐Size and Consistency with Bent's Rule

Paul

2024

ChemPhysChem

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A DFT‐based computational study is carried out to delve into the interplay between hyperconjugation and rehybridization effects underlying the formation of blue‐ or red‐shifting H‐bonds (HBs) in 1:1 complexes of cyclic ethers (HB acceptor) of varying ring‐size with haloforms, CHF3 and CHCl3 (HB donor). The calculations reveal that with decreasing angular strain (increasing ring‐size) of the cyclic ethers, the extent of blue‐shift increases for 1:1 complexes with CHF3, while a reverse sequence is observed with CHCl3, eventually leading to a red‐shifting HB in the oxepane:CHCl3 complex. It is noted that the trend in the shift of C‐H stretching fundamental is not mirrored by the C‐H bond length or interaction energies for both the systems studied, that is, the low sensitivity of the changes on the strain on the O‐atom of HB acceptor (cyclic ethers) is to be emphasized.

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A computational assessment of the O−H⋅⋅⋅O intramolecular hydrogen-bonding in substituted phenalenes: diverse degrees of covalence

Paul¹,

Rakshit²

2023

Monatsh Chem

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Lack of resonance assistance in a classical intramolecular hydrogen bond: An exploration from quantum theory of atoms‐in‐molecules perspective

Cited by 6 publications

References 54 publications

Tuning the Strength of the Resonance-Assisted Hydrogen Bond in Acenes and Phenacenes with Two o-Hydroxyaldehyde Groups—The Importance of Topology

Tuning the Strength of the Resonance-Assisted Hydrogen Bond in Acenes and Phenacenes with Two o-Hydroxyaldehyde Groups—The Importance of Topology

Blue‐ and Red‐Shifting C−H⋯O Hydrogen Bonds of Cyclic Ethers with Haloforms: Effect of Ring‐Size and Consistency with Bent's Rule

A computational assessment of the O−H⋅⋅⋅O intramolecular hydrogen-bonding in substituted phenalenes: diverse degrees of covalence

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