Estimating the energy of intramolecular bifurcated (three-centered) hydrogen bond by X-ray, IR and 1 H NMR spectroscopy, and QTAIM calculations

Afonin, A. V.; Sterkhova, Irina V.; Vashchenko, Alexander V.; Sigalov, M. V.

doi:10.1016/j.molstruc.2018.02.106

Cited by 29 publications

(23 citation statements)

References 98 publications

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“…First of all, it should be noted that the InterMHB energy can be directly determined through the experimental measurements or estimated by theoretical calculations, whereas the energy of the IntraMHB cannot be experimentally determined or theoretical calculated in any way. In the Afonin et al, we defined the energy of an IntraMHB as the hypothetical value of the negative contribution to the total energy of the molecule, equal to the energy required for the complete separation of the interacting partners, if such a separation could be possible without destroying the molecule or substantial distortion of its geometry. Thus, the magnitude of the IntraMHB energy lies outside the scale of real numbers, whereas the magnitude of the InterMHB energy is a real value.…”

Section: Resultsmentioning

confidence: 99%

“…According to the adopted classification, there are weak (1‐4 kcal mol −1 ), moderate (4‐15 kcal mol −1 ), and strong (15‐40 kcal mol −1 ) H‐bonds . In the previous papers, we categorized the strength of the N–H···O, bifurcated N–H···O···H–N, and C–H···N H‐bonds in the energy scale. In this work, we categorize the strength of the O–H···O=C H‐bond in the compounds under study.…”

Section: Resultsmentioning

confidence: 99%

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Benchmark calculations of intramolecular hydrogen bond energy based on molecular tailoring and function‐based approaches: Developing hybrid approach

Afonin

Vashchenko

2019

Int J of Quantum Chemistry

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The energy of the intramolecular hydrogen bond has been recognized and may be estimated by the molecular fragmentation method and the method based on the functional dependence on the hydrogen bond descriptor. Both basic methods for estimating the energy of intramolecular hydrogen bonds are compared using a series of the hydroxycarbonyl aliphatic compounds as the benchmark. The functional dependencies are established that provide the best fit with the molecular fragmentation method. As both methods for estimating the energy of an intramolecular hydrogen bond have disadvantages, a new hybrid approach is proposed. In this approach, the average value of the intramolecular hydrogen bond energy calculated by the molecular fragmentation method and functional dependence method is used as the estimated parameter. The hybrid approach provides a compensation of the error in the evaluation of the interaction strength compared to the molecular fragmentation method or the functional dependencies method. Hence, it allows one to more reliably rank the strength of the intramolecular hydrogen bond in homogeneous series of molecules. Based on this approach, the strength of the О−Н···О=C intramolecular hydrogen bond in the studied compounds are classified in the energy scale in terms of weak, moderate, and strong interactions.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Benchmark calculations of intramolecular hydrogen bond energy based on molecular tailoring and function‐based approaches: Developing hybrid approach

Afonin

Vashchenko

2019

Int J of Quantum Chemistry

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“…The 1 H-NMR spectroscopy is the most common tool to measure the propensity of compounds to form IMHBs, nevertheless, up to now the throughput of NMR, and other traditional methods, is limited in obtaining structure–activity relationships (SAR) and driving rapid cycles of compound optimization [8]. However, current computational chemistry allows one to assess, theoretically, the strength of IMBH through parameters such as the distance hydrogen-acceptor, the distance donor-acceptor, and the hydrogen bond angle [9]. Among the theoretical estimated parameters for the HB interaction, those from Natural Bond Orbital (NBO) and Quantum Theory of Atoms in Molecules (QTAIM) analysis [9,10,11,12,13] are the most popular.…”

Section: Introductionmentioning

confidence: 99%

“…However, current computational chemistry allows one to assess, theoretically, the strength of IMBH through parameters such as the distance hydrogen-acceptor, the distance donor-acceptor, and the hydrogen bond angle [9]. Among the theoretical estimated parameters for the HB interaction, those from Natural Bond Orbital (NBO) and Quantum Theory of Atoms in Molecules (QTAIM) analysis [9,10,11,12,13] are the most popular. In this field, DFT methodologies have proven to be valuable tools to calculate molecular properties with an appreciably low computational time demand compared with ab initio methodologies.…”

Section: Introductionmentioning

confidence: 99%

Assessing Parameter Suitability for the Strength Evaluation of Intramolecular Resonance Assisted Hydrogen Bonding in o-Carbonyl Hydroquinones

et al. 2019

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Intramolecular hydrogen bond (IMHB) interactions have attracted considerable attention due to their central role in molecular structure, chemical reactivity, and interactions of biologically active molecules. Precise correlations of the strength of IMHB’s with experimental parameters are a key goal in order to model compounds for drug discovery. In this work, we carry out an experimental (NMR) and theoretical (DFT) study of the IMHB in a series of structurally similar o-carbonyl hydroquinones. Geometrical parameters, as well as Natural Bond Orbital (NBO) and Quantum Theory of Atoms in Molecules (QTAIM) parameters for IMHB were compared with experimental NMR data. Three DFT functionals were employed to calculated theoretical parameters: B3LYP, M06-2X, and ωB97XD. O…H distance is the most suitable geometrical parameter to distinguish among similar IMHBs. Second order stabilization energies ΔEij(2) from NBO analysis and hydrogen bond energy (EHB) obtained from QTAIM analysis also properly distinguishes the order in strength of the studied IMHB. ΔEij(2) from NBO give values for the IMHB below 30 kcal/mol, while EHB from QTAIM analysis give values above 30 kcal/mol. In all cases, the calculated parameters using ωB97XD give the best correlations with experimental 1H-NMR chemical shifts for the IMHB, with R2 values around 0.89. Although the results show that these parameters correctly reflect the strength of the IMHB, when the weakest one is removed from the analysis, arguing experimental considerations, correlations improve significantly to values around 0.95 for R2.

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“…Of particular interest are bifurcated hydrogen bonds, which were known in crystals since the middle of the last century, although the possibility of their formation in solution was disputable for a long time . At present, the existence of bifurcated hydrogen bonds in solution is proved by theoretical and experimental studies . Nevertheless, further investigations are needed to address the following issues: (1) the effect of self‐association and solvation (both specific and nonspecific) favoring or disfavoring the retention of bifurcated hydrogen bonds and (2) synergistic or antagonistic influence of intermolecular hydrogen bonding on the components of the existing intramolecular hydrogen bond.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular and intermolecular bifurcated hydrogen bonds in 2‐pyrrolyl‐7‐hydroxy‐2‐methylidene‐2,3‐dihydro‐1H‐inden‐1‐one

Chípanina

Oznobikhina

Sigalov

et al. 2018

J of Physical Organic Chem

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Cyclic and linear dimers as well as the solvate H-bonded complexes of the Z and E isomers of 2-pyrrolyl-7-hydroxy-2-methylidene-2,3-dihydro-1H-inden-1one 1 were investigated by theoretical calculations, and their formation was proved by FT-IR and UV spectroscopy. In dimers, both strengthening and weakening of the intramolecular component of the bifurcated hydrogen bond are observed depending on the type of the formed intermolecular hydrogen bond. The effect of proton donors MeOH, HCN, and proton acceptor DMSO on the intramolecular components in solvent H-bonded complexes is discussed. A larger energy gap in the 1-E than in 1-Z isomer allows to predict photoinduced isomeric transition 1-Е → 1-Z in nonpolar aprotic solvents.

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Estimating the energy of intramolecular bifurcated (three-centered) hydrogen bond by X-ray, IR and 1 H NMR spectroscopy, and QTAIM calculations

Cited by 29 publications

References 98 publications

Benchmark calculations of intramolecular hydrogen bond energy based on molecular tailoring and function‐based approaches: Developing hybrid approach

Benchmark calculations of intramolecular hydrogen bond energy based on molecular tailoring and function‐based approaches: Developing hybrid approach

Assessing Parameter Suitability for the Strength Evaluation of Intramolecular Resonance Assisted Hydrogen Bonding in o-Carbonyl Hydroquinones

Intramolecular and intermolecular bifurcated hydrogen bonds in 2‐pyrrolyl‐7‐hydroxy‐2‐methylidene‐2,3‐dihydro‐1H‐inden‐1‐one

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