Intramolecular OHO bonding in dibenzoylmethane: symmetry and spectral manifestations

Petković, Milena; Etinski, Mihajlo

doi:10.1039/c4ra05586a

Cited by 19 publications

(31 citation statements)

References 78 publications

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“…A more detailed analysis of vibrational properties would involve inclusion of anharmonicity, which would most likely result in construction of high‐dimensional models. This is usually the case for systems with bridges that connect distinct atoms, like in hydrogen bonded systems …”

Section: Resultsmentioning

confidence: 99%

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Control of a photoswitching chelator by metal ions:DFT,NBO, andQTAIManalysis

Dimić

Petković

2015

Int J of Quantum Chemistry

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Ability of aroylhydrazones to change conformation upon interaction with light makes them promising candidates for molecular switches. Isomerization can be controlled through complexation with selected metal ions which bind with different affinity. N′‐[1‐(2‐hydroxyphenyl)ethyliden]iso‐nicotinoylhydrazide (HAPI) is an example of a dual‐wavelenght photoswitching molecule, whose complexation with metal ions was recently experimentally investigated (Franks et al. J. Inorg. Chem. 2014, 53, 1397). In this contribution, complexes between HAPI and K+, Ca2+, Mn2+, Fe2+, Fe3+, Cu+, Cu2+, and Zn2+ ions were investigated using Density Functional Theory, Natural Bond Order analysis, and Quantum Theory of Atoms in Molecules. The most important parameters that determine complex stability are found to be ion radius and charge transferred from ligands to the ion: smaller ion radii and larger CT values characterize formation of more stable complexes. Our results explain experimentally observed effect of different metal ions on photoisomerization through determination of metal ion affinity (MIA): photoisomerization is inhibited if MIA exceeds 100 kcal/mol; for MIA between 50 and 100 kcal/mol excess of metal ions prevents isomerization, whereas in case of MIA below 50 kcal/mol metal ions have no influence on light–HAPI interaction. © 2015 Wiley Periodicals, Inc.

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Section: Resultsmentioning

confidence: 99%

“…This is usually the case for systems with bridges that connect distinct atoms, like in hydrogen bonded systems. [36][37][38][39][40][41] Thermodynamic properties and metal ion affinity…”

Section: Full Papermentioning

confidence: 99%

Control of a photoswitching chelator by metal ions:DFT,NBO, andQTAIManalysis

Dimić

Petković

2015

Int J of Quantum Chemistry

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“…[10,[15][16][17][18][19][20][21][22][23][24][25][26][27][28] The perplexity caused by the relative stability of the asymmetric and symmetric DBM's protic tautomers is due to the inability of experimental scattering and spectroscopic techniques to resolve ultrafast proton motion in the hydrogen bond, but also possibly due to various experimental conditions and aggregate states in which DBM was studied. [10,[15][16][17][18][19][20][21][22][23][24][25][26][27][28] The perplexity caused by the relative stability of the asymmetric and symmetric DBM's protic tautomers is due to the inability of experimental scattering and spectroscopic techniques to resolve ultrafast proton motion in the hydrogen bond, but also possibly due to various experimental conditions and aggregate states in which DBM was studied.…”

Section: The Effects Of Hydrogen Bonding and Homogeneous Electric Fiementioning

confidence: 99%

“…[23,26] The potential energy barrier for the proton transfer in the gas phase was estimated to be approximately between 1 and 2 kcal/mol [22] and free energy calculations [22,26] favored the asymmetric over the symmetric tautomer. [22] We further examined to what extent the symmetry of the profile is altered when DBM interacts with a methanol molecule by the O···HÀ O m and O···HÀ C m hydrogen bonds (methanol groups are labeled with the index m). The barrier was found to be 1.6 kcal/mol.…”

Section: The Effects Of Hydrogen Bonding and Homogeneous Electric Fiementioning

confidence: 99%

“…Enolic DBM attracted a lot of experimental and theoretical attention due to a conflicting assignment of its intramolecular hydrogen bond structure. [10,[15][16][17][18][19][20][21][22][23][24][25][26][27][28] The perplexity caused by the relative stability of the asymmetric and symmetric DBM's protic tautomers is due to the inability of experimental scattering and spectroscopic techniques to resolve ultrafast proton motion in the hydrogen bond, but also possibly due to various experimental conditions and aggregate states in which DBM was studied. [23,26] The potential energy barrier for the proton transfer in the gas phase was estimated to be approximately between 1 and 2 kcal/mol [22] and free energy calculations [22,26] favored the asymmetric over the symmetric tautomer.…”

Section: The Effects Of Hydrogen Bonding and Homogeneous Electric Fiementioning

confidence: 99%

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Elucidating Solvent Effects on Strong Intramolecular Hydrogen Bond: DFT‐MD Study of Dibenzoylmethane in Methanol Solution

et al. 2019

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The dynamic aspect of solvation plays a crucial role in determining properties of strong intramolecular hydrogen bonds since solvent fluctuations modify instantaneous hydrogen-bonded proton transfer barriers. Previous studies pointed out that solvent-solute interactions in the first solvation shell govern the position of the proton but the ability of the electric field due to other solvent molecules to localize the proton remains an important issue. In this work, we examine the structure of the OÀ H···O intramolecular hydrogen bond of dibenzoylmethane in methanol solution by employing density functional theory-based molecular dynamics and quantum chemical calculations. Our computations showed that homoge-neous electric fields with intensities corresponding to those found in polar solvents are able to considerably alter the proton transfer barrier height in the gas phase. In methanol solution, the proton position is correlated with the difference in electrostatic potentials on the oxygen atoms of dibenzoylmethane even when dibenzoylmethane-methanol hydrogen bonding is lacking. On a timescale of our simulation, the hydrogen bonding and solvent electrostatics tend to localize the proton on different oxygen atoms. These findings provide an insight into the importance of the solvent electric field on the structure of a strong intramolecular hydrogen bond.

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Unusual H‐Bond Topology and Bifurcated H‐bonds in the 2‐Fluoroethanol Trimer

et al. 2015

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By using a combination of rotational spectroscopy and ab initio calculations, an unusual H‐bond topology was revealed for the 2‐fluoroethanol trimer. The trimer exhibits a strong heterochiral preference and adopts an open OH⋅⋅⋅OH H‐bond topology while utilizing two types of bifurcated H‐bonds involving organic fluorine. This is in stark contrast to the cyclic OH⋅⋅⋅OH H‐bond topology adopted by trimers of water and other simple alcohols. The strengths of different H‐bonds in the trimer were analyzed by using the quantum theory of atoms in molecules. The study showcases a remarkable example of a chirality‐induced switch in H‐bond topology in a simple transient chiral fluoroalcohol. It provides important insight into the H‐bond topologies of small fluoroalcohol aggregates, which are proposed to play a key role in protein folding and in enantioselective reactions and separations where fluoroalcohols serve as a (co)solvent.

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Intramolecular OHO bonding in dibenzoylmethane: symmetry and spectral manifestations

Abstract: Calculations reveal that both symmetric and asymmetric structures of dibenzoylmethane are present in the gas phase at room temperature.

Cited by 19 publications

References 78 publications

Control of a photoswitching chelator by metal ions:DFT,NBO, andQTAIManalysis

Control of a photoswitching chelator by metal ions:DFT,NBO, andQTAIManalysis

Elucidating Solvent Effects on Strong Intramolecular Hydrogen Bond: DFT‐MD Study of Dibenzoylmethane in Methanol Solution

Unusual H‐Bond Topology and Bifurcated H‐bonds in the 2‐Fluoroethanol Trimer

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