Molecular Docking via Olefinic OH···π Interactions: A Bulky Alkene Model System and Its Cooperativity

Medel, Robert; Heger, Matthias; Suhm, Martin A.

doi:10.1021/jp508424p

Cited by 22 publications

(22 citation statements)

References 49 publications

(101 reference statements)

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“…The red shi of the OH-stretching fundamental transition of TFE-CMP was obtained to be 52 cm À1 . This result is in line with early studies of the O-H/p hydrogen bonding interactions: (i) the harmonic red shis of the OH-stretching fundamental transition of t-butyl alcohol with cyclohexene, cyclopentene and norbornene were observed at 63 to 80 cm À1 in supersonic jet expansions; 28 (ii) in an FTIR spectroscopic study of the MeOH-ethene complex, the red shi of the OH-stretching fundamental transition of MeOH was observed at 45 cm À1 .…”

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confidence: 91%

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Weak hydrogen bonding competition between O–H⋯π and O–H⋯Cl

et al. 2017

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The weak intermolecular interaction between 2,2,2-trifluoroethanol (TFE) and 3-chloro-2-methyl-1-propene (CMP) has been investigated by gas phase FTIR spectroscopy and DFT calculations. CMP offers two hydrogen bond docking sites to the hydrogen bond donor: the chlorine atom (O-H/Cl) and the C]C p electron system (O-H/p). DFT calculations suggest that MeOH approaches CMP in five different orientations. The structural, energetic, and spectroscopic parameters of the most stable structures in each orientation were studied, and their binding energies range from À25.5 to À19.5 kJ mol À1. The docking to the p system is at least 1 kJ mol À1 more favored than the docking to the chlorine atom. The equilibrium constant for complexation (2.3 Â 10 À2 ) was determined from the experimental and calculated intensity of the OH-stretching transition. The Gibbs free energy of formation was found to be 9.3 kJ mol À1. The nature of the non-covalent interaction was analyzed with the atoms in molecules (AIM) method.

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confidence: 91%

“…[2][3][4][5][6] The hydrogen bonded methanol-ethene complex, the most elementary example of weak intermolecular alcohol hydrogen bonding to a p system, has been studied recently with FTIR spectroscopy.…”

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confidence: 99%

Weak hydrogen bonding competition between O–H⋯π and O–H⋯Cl

et al. 2017

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“…37 A comparison of the calculated binding energies (cf. 80 In the spectral window between the OH stretching fundamental of the t-BuOH monomer (3642 cm…”

Section: Theoretical Resultsmentioning

confidence: 99%

“…3, spectral scaling to matching monomer transitions (ref. 80 and unpublished work, 2687 cm À1 for t-BuOD) suggests that the persisting middle peak is indeed due to an OH-O isomer, whereas the higher wavenumber peak is not. Looking at relative intensities and considering the twice larger predicted absorption cross-section of the OH-O isomer (cf.…”

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confidence: 86%

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Multi-spectroscopic and theoretical analyses on the diphenyl ether–tert-butyl alcohol complex in the electronic ground and electronically excited state

Bernhard

Dietrich

Fatima

et al. 2017

Phys. Chem. Chem. Phys.

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a Aromatic ethers such as diphenyl ether (DPE) represent molecules with different docking sites for alcohols leading to competing OH-O and OH-p interactions. In a multi-spectroscopic approach in combination with quantum chemical calculations the complex of DPE with tert-butyl alcohol (t-BuOH) is investigated in the electronic ground state (S 0 ) and the electronically excited state (S 1 ). FTIR, microwave as well as mass-and isomer-selective IR/R2PI spectra are recorded, revealing co-existing OH-O and OH-p isomers in the S 0 state. Surprisingly, they are predicted to be of almost equal stability in contrast to the previously investigated DPE-MeOH complex, where the OH-p structure is preferred by both theory and experiment. The tert-butyl group in t-BuOH allows for a simultaneous optimization of hydrogen-bonding and dispersion interactions, which provides a sensitive meeting point between theory and experiment. In the electronically excited state of DPE-t-BuOH, vibrational spectra could be recorded separately for both isomers using UV/IR/UV spectroscopy. In the S 1 state the same structural binding motifs are obtained as in the S 0 state with the OH-O bond being weakened for the OH-O arrangement and the OH-p interaction being strengthened in the case of the OH-p isomer compared to the S 0 state.

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Vibrational Signatures of Chirality Recognition Between α‐Pinene and Alcohols for Theory Benchmarking

2019

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Chirality recognition between largely rigid molecules can be applied as ab enchmark for the description of intermolecular forces by theoretical methods,b ecause one constituent is merely mirrored, so other deficits of the methods such as neglect of anharmonicity should mostly cancel. To test this approach, mixed OH···p-bridged dimers between the enantiomers of the bicyclic monoterpene a-pinene and the chiral secondary alcohols borneol, a-fenchol, isopinocampheol, and 1-phenylethanol were formed in as upersonic jet and probed by linear FTIR spectroscopy. With borneol and afenchol, pronounced shifts in the hydroxyl stretching frequencies upon exchange of the handedness are observed. From three tested density functionals,only B3LYP-D3(BJ) is able to predict these diastereomeric shifts in as atisfactory manner, while M06-2X and wB97X-D fall short.Chirality recognition, the ability of chiral objects to distin-Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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Molecular Docking via Olefinic OH···π Interactions: A Bulky Alkene Model System and Its Cooperativity

Cited by 22 publications

References 49 publications

Weak hydrogen bonding competition between O–H⋯π and O–H⋯Cl

Weak hydrogen bonding competition between O–H⋯π and O–H⋯Cl

Multi-spectroscopic and theoretical analyses on the diphenyl ether–tert-butyl alcohol complex in the electronic ground and electronically excited state

Vibrational Signatures of Chirality Recognition Between α‐Pinene and Alcohols for Theory Benchmarking

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