Competing hydrogen bond topologies in 2-fluoroethanol dimer

Scharge, Tina; Emmeluth, Corinna; Häber, Thomas; Suhm, Martin A.

doi:10.1016/j.molstruc.2005.09.022

Cited by 28 publications

(49 citation statements)

References 31 publications

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“…[13] The current study also supports the previous conclusion that i j c j het is Table 3. The calculated donor and acceptor distortion energies and the interaction energies for the six most stable dimeric FE conformers.…”

Section: Discussionsupporting

confidence: 90%

“…For example, i j c j het means that the conformer has an inserted intermolecular hydrogen-bond ring, with the two binding partners in the compact relative orientation, and is heterochiral. This labelling scheme is the same as that used in reference [13].…”

Section: Resultsmentioning

confidence: 99%

“…A similar conclusion was obtained from the lower level MP2/6-311 + G* calculations. [13] To understand the more subtle molecular recognition among the dimeric conformers observed is, however, more challenging. The energy span of the six most stable dimeric conformers built out of the G + gÀ/GÀg + FE subunits is on the order of 2 kJ mol À1 or about 10 % of the total binding energy at the MP2/6-311 + + gA C H T U N G T R E N N U N G (d,p) level of theory.…”

Section: Discussionmentioning

confidence: 99%

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Molecular Self‐Recognition: Rotational Spectra of the Dimeric 2‐Fluoroethanol Conformers

Liu

Borho

2008

Chemistry A European J

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Fluoroalcohols show competitive formation of intra- and intermolecular hydrogen bonds, a property that may be crucial for the protein-altering process in a fluoroalcohol/water solution. In this study, we examine the intra- and intermolecular interactions of 2-fluoroethanol (FE) in its dimeric conformers by using rotational spectroscopy and ab initio calculations. Three pairs of homo- and heterochiral dimeric FE conformers are predicted to be local minima at the MP2/6-311++G(d,p) level of theory. They are solely made of the slightly distorted most stable G+g-/G-g+ FE monomer units. Jet-cooled rotational spectra of four out of the six predicted dimeric conformers were observed and unambiguously assigned for the first time. All four observed dimeric conformers have compact geometries in which the fluoromethyl group of the acceptor tilts towards the donor and ensures a large contact area. Experimentally, the insertion of the O-H group of one FE subunit into the intramolecular O-H...F bond of the other was found to lead to a higher stabilisation than the pure association through an intermolecular O-H...O-H link. The hetero- and homochiral combinations were observed to be preferred in the inserted and the associated dimeric conformers, respectively. The experimental rotational constants and the stability ordering are compared with the ab initio calculations at the MP2 level with the 6-311++G(d,p) and aug-cc-pVTZ basis sets. The effects of fluorination and the competing inter- and intramolecular hydrogen bonds on the stability of the dimeric FE conformers are discussed.

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Section: Discussionsupporting

confidence: 90%

Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

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Molecular Self‐Recognition: Rotational Spectra of the Dimeric 2‐Fluoroethanol Conformers

Liu

Borho

2008

Chemistry A European J

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“…MFE dimers occur in two hydrogen-bond topologies, with the more stable one being of the inserted type. [165] In this system, there appears to be a slight preference for opposite helicity in the two building blocks. Owing to the ms or longer timescale of the stereomutation process in MFE monomers, [194] MFE dimers may be considered as a case of chirality discrimination.…”

Section: Methodsmentioning

confidence: 87%

“…[113] While the two gauche forms are equivalent in 2-chloroethanol or 2-fluoroethanol, [165] replacement of one C a -H atom by a methyl group breaks this symmetry and favors one gauche form over the other. In methyl amino ethanol, [125] the three different N-substituents form a transient stereocenter, which is stabilized by an internal OH···N hydrogen bond.…”

Section: Intramolecular Counterparts Of Chirality Inductionmentioning

confidence: 99%

Chirality Recognition between Neutral Molecules in the Gas Phase

2008

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Noncovalent interactions are particularly intriguing when they involve chiral molecules, because the interactions change in a subtle way upon replacing one of the partners by its mirror image. The resulting phenomena involving chirality recognition are relevant in the biosphere, in organic synthesis, and in polymer design. They may be classified according to the permanent or transient chirality of the interacting partners, leading to chirality discrimination, chirality induction, and chirality synchronization processes. For small molecules, high-level quantum chemical calculations for such processes are feasible. To provide reliable connections between theory and experiment, such phenomena are best studied in vacuum isolation at low temperature, using rotational, vibrational, electronic, and photoionization spectroscopy. We review these techniques and the results which have become available in recent years, with special emphasis on dimers of permanently chiral molecules and on the influence of conformational flexibility. Analogies between the microscopic mechanisms and macroscopic phenomena and between intra- and intermolecular cases are drawn.

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Hydrogen Bond Dynamics in Alcohol Clusters

Suhm

2008

Advances in Chemical Physics

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Competing hydrogen bond topologies in 2-fluoroethanol dimer

Cited by 28 publications

References 31 publications

Molecular Self‐Recognition: Rotational Spectra of the Dimeric 2‐Fluoroethanol Conformers

Molecular Self‐Recognition: Rotational Spectra of the Dimeric 2‐Fluoroethanol Conformers

Chirality Recognition between Neutral Molecules in the Gas Phase

Hydrogen Bond Dynamics in Alcohol Clusters

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