Molecular tailoring approach as tool for revealing resonance‐assisted hydrogen bond: Case study of <scp><i>Z</i></scp>‐pyrrolylenones with the NH⋯OС intramolecular hydrogen bond

Afonin, A. V.; Rusinska-Roszak, Danuta

doi:10.1002/jcc.26960

Cited by 4 publications

(7 citation statements)

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“…For the compounds with a bifurcated H-bond, the fragmentation scheme includes six fragments to account for both H-bonds (see Scheme S1, Supplementary Materials , p. S2). It was recognized that the RAHB is implemented only if the 4n + 2 Hückel aromaticity rule is fulfilled for π-conjugated chain [ 60 ]. In the rightmost compound in Scheme 1 , the eight electrons take part in π-conjugation, so this compound is of the non-RAHB type.…”

Section: Resultsmentioning

confidence: 99%

“…The second method for quantifying the IMHB energy is the molecular tailoring approach (MTA), which is based on the fragmentation of molecules ( vide infra ). Currently, this method is effectively employed to evaluate the IMHB energy in medium and large molecules [ 37 , 38 , 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 ].…”

Section: Introductionmentioning

confidence: 99%

“…RAHB is a complex interaction, consisting of σ- and π-components, which are responsible for the H-bond per se and resonance assistance, respectively. Application of the FBA method allows the energy of the RAHB σ-component to be estimated since this method is based on the properties of the σ-skeleton of molecules [ 37 , 38 , 60 ]. The MTA method estimates the total energy of intramolecular RAHB [ 38 , 60 ].…”

Section: Introductionmentioning

confidence: 99%

“…Application of the FBA method allows the energy of the RAHB σ-component to be estimated since this method is based on the properties of the σ-skeleton of molecules [ 37 , 38 , 60 ]. The MTA method estimates the total energy of intramolecular RAHB [ 38 , 60 ]. The difference between the RAHB energies, quantified by the FBA and MTA methods, gives an estimation of the π-contribution to the total RAHB energy [ 38 , 60 ].…”

Section: Introductionmentioning

confidence: 99%

“…The MTA method estimates the total energy of intramolecular RAHB [ 38 , 60 ]. The difference between the RAHB energies, quantified by the FBA and MTA methods, gives an estimation of the π-contribution to the total RAHB energy [ 38 , 60 ]. In this way, the separation of the total RAHB energy into σ- and π-components was successfully carried out for classical RAHB structures such as β-diketones [ 38 ].…”

Section: Introductionmentioning

confidence: 99%

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Revealing the Reasons for Degeneration of Resonance-Assisted Hydrogen Bond on the Aromatic Platform: Calculations of Ortho-, Meta-, Para-Disubstituted Benzenes, and (Z)-(E)-Olefins

Afonin

Rusinska-Roszak

2023

Molecules

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The energies of the O−H∙∙∙O=C intramolecular hydrogen bonds were compared quantitatively for the series of ortho-disubstituted benzenes and Z-isomers of olefins via a molecular tailoring approach. It was established that the hydrogen bond energy in the former series is significantly less than that in the latter one. The reason for lowering the hydrogen bond energy in the ortho-disubstituted benzenes compared to the Z-isomers of olefins is the decrease in the π-contribution to the total energy of the complex interaction, in which the hydrogen bond per se is enhanced by the resonance effect. By the example of the para- and meta-disubstituted benzenes, as well as E-isomers of olefins, it was explicitly shown that the aromatic ring is a much poorer conductor of the resonance effect compared to the double bond. The hydrogen bond in the ortho-disubstituted benzenes has a lower energy than a typical resonance-assisted hydrogen bond because the aromatic moiety cannot properly assist the hydrogen bond with a resonance effect. Thus, a hydrogen bond on an aromatic platform should fall into a special category, namely an aromaticity-assisted hydrogen bond, which is closer by nature to a simple hydrogen bond rather than to a resonance-assisted one.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Revealing the Reasons for Degeneration of Resonance-Assisted Hydrogen Bond on the Aromatic Platform: Calculations of Ortho-, Meta-, Para-Disubstituted Benzenes, and (Z)-(E)-Olefins

Afonin

Rusinska-Roszak

2023

Molecules

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Quantification of hydrogen bond energy based on equations using spectroscopic, structural, QTAIM-based, and NBO-based descriptors which calibrated by the molecular tailoring approach

Afonin,

Rusinska-Roszak

2023

J Mol Model

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Context Hydrogen bonds critically influence the structure and properties of both organic molecules and biomolecules, as well as supramolecular assemblies. For this reason, the development and elaboration of methods for quantitative assessment of hydrogen bond energy is an urgent challenge. In this study, using a large series of hydroxycarbonyl aliphatic compounds with the O‒H···O = C intramolecular hydrogen bond, a bank of hydrogen bond descriptors was created, including spectroscopic, structural, QTAIM-based, and NBO-based parameters. It was shown that the O‒H vibration frequency, OH chemical shift as the spectroscopic descriptors, the O···H hydrogen bond length, O···O distance, and O‒H covalent bond length as the structural descriptors, the electron density and its Laplacian, electron potential energy density in the hydrogen bond critical point, the electron density at the ring critical point as the QTAIM-based descriptors change in a correlated manner. The same correlation is found in change of the charge transfer energy through a hydrogen bond, the occupancy of the O‒H bond antibonding orbital, the Wiberg indices of the O···H hydrogen bond, and the O‒H covalent bond, as well as the polarization of the O‒H bond, which are the NBO-based descriptors. It was also recognized that the specified descriptors from the spectroscopic, structural, QTAIM-based, and NBO-based categories are functionally related to the values of intramolecular hydrogen bond energy, quantified via the molecular tailoring approach. This allowed one to obtain a system of equations for quantitative estimation of intramolecular hydrogen bond energy based on the spectroscopic, structural, QTAIM, and NBO descriptors, which makes such quantification more dependable and reliable. Methods To obtain the spectroscopic descriptors, the vibrational spectra and shielding constants were calculated using the GIAO method. Structural descriptors were obtained for the equilibrium geometry of molecules, calculated at the MP2(FC)/6–311 + + (2d,2p) level using the Gaussian 09 program. The QTAIM-based descriptors were calculated using the AIMAll program within the framework of the quantum theory “Atoms in Molecules.” The NBO-based descriptors were calculated using the NBO 3.1 program implemented into Gaussian 09. To quantify the energy of intramolecular hydrogen bonds, molecular fragmentation was used within the molecular tailoring approach.

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Theoretical studies on the interaction of HXeF with M3N3H6 (M = B, Al and Ga) and their substituted derivatives

Song,

Chen

2023

Chemical Physics Letters

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Molecular tailoring approach as tool for revealing resonance‐assisted hydrogen bond: Case study of Z‐pyrrolylenones with the NH⋯OС intramolecular hydrogen bond

Cited by 4 publications

References 77 publications

Revealing the Reasons for Degeneration of Resonance-Assisted Hydrogen Bond on the Aromatic Platform: Calculations of Ortho-, Meta-, Para-Disubstituted Benzenes, and (Z)-(E)-Olefins

Revealing the Reasons for Degeneration of Resonance-Assisted Hydrogen Bond on the Aromatic Platform: Calculations of Ortho-, Meta-, Para-Disubstituted Benzenes, and (Z)-(E)-Olefins

Quantification of hydrogen bond energy based on equations using spectroscopic, structural, QTAIM-based, and NBO-based descriptors which calibrated by the molecular tailoring approach

Theoretical studies on the interaction of HXeF with M3N3H6 (M = B, Al and Ga) and their substituted derivatives

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