Subtle hydrogen bonds: benchmarking with OH stretching fundamentals of vicinal diols in the gas phase

Hartwig, Beppo; Suhm, Martin A.

doi:10.1039/d1cp03367k

Cited by 11 publications

(44 citation statements)

References 96 publications

(152 reference statements)

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“…The IR absorption spectra in the OH-stretching region looks more interesting since it exhibits a sharp feature at 3612 cm −1 , common to all three compounds, and a broad feature at 3542 cm −1 in all three compounds, plus another broad hump centered at 3487 cm −1 for 1 . Following Paoloni et al [ 32 ] (see also the more recent work by Hartwig and Suhm [ 37 ]), who carefully investigated the cases of diols, we think that the 3612 cm −1 is due to the OH-stretching in either the 3- or 9- position acting as an acceptor of H-bond and behaving almost as an OH-stretching “free” from H-bond. We believe the 3542 cm −1 feature instead to be due to OH stretching in donor intramolecular H-bonding for the 3 position (common to 1 , 2, and 3 ) and the 3487 cm −1 feature to be due to OH stretching in donor intramolecular H-bonding for the 9 position (present only in 1 ).…”

Section: Resultsmentioning

confidence: 73%

The Assignment of the Absolute Configuration of Non-Cyclic Sesquiterpenes by Vibrational and Electronic Circular Dichroism: The Example of Chiliadenus lopadusanus Metabolites

Mazzeo

Cimmino²,

Longhi

et al. 2021

Biomolecules

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9-Hydroxynerolidol, 9-oxonerolidol, and chiliadenol B are three farnesane-type sesquiterpenoids isolated from Chiliadenus lopadusanus that have shown an interesting activity against human pathogens as Gram+ and Gram− bacteria resistant to antibiotics. However, the absolute configuration (AC) of these interesting sesquiterpenes has not been assigned so far. Vibrational and electronic circular dichroism spectra have been recorded and correlations are pointed out for the three compounds. Density functional theory (DFT) calculations are used in conjunction with Mosher’s method of investigation to assign AC. Statistical analysis is considered to quantitatively define the choice of AC from VCD spectra.

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Section: Resultsmentioning

confidence: 73%

The Assignment of the Absolute Configuration of Non-Cyclic Sesquiterpenes by Vibrational and Electronic Circular Dichroism: The Example of Chiliadenus lopadusanus Metabolites

Mazzeo

Cimmino²,

Longhi

et al. 2021

Biomolecules

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“…For systems bridged in such a way no other ring sizes have been To distinguish between the many different conformers a few extra signifiers are added to the shorthand notation which have been previously discussed in Refs. [18,165]. These are illustrated in Fig.…”

Section: 2-diol Monomersmentioning

confidence: 98%

“…Given the large amount of molecules studied in this work, systematic abbreviations for the different systems are introduced which have previously been laid out in Ref. [165]. The different systems are classified according to the substitution geminal to each OH group.…”

Section: 2-diol Monomersmentioning

confidence: 99%

“…The symmetrical diols ethane-1,2-diol (0-0) [18,166] , cyclohexanediol-1,2-diol (t6-6) [166] and pinacol (MM-MM) [165] lend themselves to initial fits since their assignment is unambiguous given the fact that only two conformers are energetically relevant, as the energy diagrams at the B3LYP/maTZ level of theory in Fig. 3.1 show.…”

Section: Initial Assignmentsmentioning

confidence: 99%

“…The results of this analysis have largely been published in Ref. [165] and will not be explicitly cited. Parts of the computed geometries at the B3LYP/maTZ level of computation have been published in Ref.…”

Section: Introductionmentioning

confidence: 99%

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Diols under Investigation: Benchmarking their Monomers, Dimers and Chirality Recognition

Hartwig¹

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Additionally, I would like to thank the institutes workshops for always helping out with any issues that came up. Here, I would like to especially thank Reinhard Hildebrandt and Mike Zippert of the mechanical workshop. The former helped to design a custom heat-exchanger and the latter helped with the acquisition of new pressure regulators. Furthermore, I would also like to thank Rainer Oswald for helping out when problems arose with the Chemie-Cluster and making quantum-chemistry programs available as modules. Thanks also go to Stefan Grimme who allowed for the use of the xTB and CREST programs on the Chemie-Cluster which have been developed by his group. Special thanks also goes to Laura N. Schiebel, for whom I had the pleasure to supervise her bachelor thesis. She also continued researching open questions of her bachelor project as a research assistant (Junior Bencher), funded by the DFG as part of the RTG. I would also like to thank her for proof-reading large parts of this work.Furthermore, I would like to thank the entire Suhm group for the great atmosphere, be it during conferences, table football games, group trips or game nights. I am also grateful I to Robert Medel for proof-reading the monomer chapter and providing computational data for tri-tert-butyl-methanol. Further thanks go to Maxim Gawrilow, Arman Nejad, Sophie Schweer and Taija Fischer for help and advise regarding experimental and nonexperimental work. Additionally, I would like to thank the entire Schnell Group for the warm welcome during my research stay in Hamburg.Last but not least, I would like to thank my family and friends for their support.

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Hydrogen‐Atom Tunneling in a Homochiral Environment

et al. 2023

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The role‐exchanging concerted torsional motion of two hydrogen atoms in the homochiral dimer of trans‐1,2‐cyclohexanediol was characterized through a combination of broadband rotational spectroscopy and theoretical modeling. The results reveal that the concerted tunneling motion of the hydrogen atoms leads to the inversion of the sign of the dipole moment components along the a and b principal axes, due to the interchange motion that cooperatively breaks and reforms one intermolecular hydrogen bond. This motion is also coupled with two acceptor switching motions. The energy difference between the two ground vibrational states arising from this tunneling motion was determined to be 29.003(2) MHz. The corresponding wavefunctions suggest that the two hydrogen atoms are evenly delocalized on two equivalent potential wells, which differs from the heterochiral case where the hydrogen atoms are confined in separate wells, as the permutation‐inversion symmetry breaks down. This intriguing contrast in hydrogen‐atom behavior between homochiral and heterochiral environments could further illuminate our understanding of the role of chirality in intermolecular interactions and dynamics.

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Subtle hydrogen bonds: benchmarking with OH stretching fundamentals of vicinal diols in the gas phase

Abstract: The theoretical description of spectral signatures for weakly bound hydrogen contacts between alcohol groups is challenging and remains poorly characterised. By combining Raman jet spectroscopy with appropriately scaled harmonic DFT...

Cited by 11 publications

References 96 publications

The Assignment of the Absolute Configuration of Non-Cyclic Sesquiterpenes by Vibrational and Electronic Circular Dichroism: The Example of Chiliadenus lopadusanus Metabolites

The Assignment of the Absolute Configuration of Non-Cyclic Sesquiterpenes by Vibrational and Electronic Circular Dichroism: The Example of Chiliadenus lopadusanus Metabolites

Diols under Investigation: Benchmarking their Monomers, Dimers and Chirality Recognition

Hydrogen‐Atom Tunneling in a Homochiral Environment

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