Dispersion-controlled docking preference: multi-spectroscopic study on complexes of dibenzofuran with alcohols and water

Bernhard, Dominic; Fatima, Mariyam; Poblotzki, Anja; Steber, Amanda L.; Pérez, Cristóbal; Suhm, Martin A.; Schnell, Melanie; Gerhards, Markus

doi:10.1039/c9cp02635e

Cited by 30 publications

(36 citation statements)

References 81 publications

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“…In the DPE complexes, an overall stabilization of the OH⋅⋅⋅O motif with increasing side‐chain size in comparison with the OH⋅⋅⋅π motif was observed because for the larger alcohols the O−H⋅⋅⋅O structure also allows for stabilization via dispersion with the phenyl rings. The trend observed in the DBF study is completely reversed, with a preference for the OH⋅⋅⋅π over the OH⋅⋅⋅O interaction with increasing alkyl‐group size. Detailed explanations of these preferences for DPE and DBF can be found in Refs.…”

Section: Resultsmentioning

confidence: 99%

“…Detailed explanations of these preferences for DPE and DBF can be found in Refs. and , respectively. The DAE and DPE complexes exhibit the O−H⋅⋅⋅O motif also for larger, more bulky binding partners because their respective adamantyl or phenyl rings can establish secondary interactions.…”

Section: Resultsmentioning

confidence: 99%

“…In the DPE‐ t BuOH (O−H⋅⋅⋅O and O−H⋅⋅⋅π) complexes, electrostatics and LD interactions contribute equally, as the aromatic rings and the alkyl groups act as DEDs. LD interactions play a crucial role becoming the most stabilizing contribution in the DBF‐ t BuOH (O−H⋅⋅⋅π) cluster . Note that the exchange‐repulsion energy values are similar for all the DAE complexes.…”

Section: Resultsmentioning

confidence: 99%

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London Dispersion and Hydrogen‐Bonding Interactions in Bulky Molecules: The Case of Diadamantyl Ether Complexes

Quesada‐Moreno

Pinacho

Pérez

et al. 2020

Chemistry A European J

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Diadamantyl ether (DAE, C20H30O) represents a good model to study the interplay between London dispersion and hydrogen‐bond interactions. By using broadband rotational spectroscopy, an accurate experimental structure of the diadamantyl ether monomer is obtained and its aggregates with water and a variety of aliphatic alcohols of increasing size are analyzed. In the monomer, C−H⋅⋅⋅H−C London dispersion attractions between the two adamantyl subunits further stabilize its structure. Water and the alcohol partners bind to diadamantyl ether through hydrogen bonding and non‐covalent Owater/alcohol⋅⋅⋅H−CDAE and C−Halcohol⋅⋅⋅H−CDAE interactions. Electrostatic contributions drive the stabilization of all the complexes, whereas London dispersion interactions become more pronounced with increasing size of the alcohol. Complexes with dominant dispersion contributions are significantly higher in energy and were not observed in the experiment. The results presented herein shed light on the first steps of microsolvation and aggregation of molecular complexes with London dispersion energy donor (DED) groups and the kind of interactions that control them.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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London Dispersion and Hydrogen‐Bonding Interactions in Bulky Molecules: The Case of Diadamantyl Ether Complexes

Quesada‐Moreno

Pinacho

Pérez

et al. 2020

Chemistry A European J

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“…31,32 More recently, jet FTIR spectroscopy has also been combined with nozzle heating. [33][34][35][36] Our own heatable jet-FTIR setup 12,37,38 was previously restricted to short double-slit nozzles with a limited column density of molecular clusters. This limitation is overcome in the present study.…”

Section: Introductionmentioning

confidence: 99%

The reduced cohesion of homoconfigurational 1,2-diols

Hartwig

Lange

Poblotzki

et al. 2020

Phys. Chem. Chem. Phys.

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By a combination of linear FTIR and Raman jet spectroscopy, racemic trans-1,2-cyclohexanediol is shown to form an energetically unrivalled S 4 -symmetric heterochiral dimer in close analogy to 1,2-ethanediol.Analogous experiments with enantiopure trans-1,2-cyclohexanediol reveal the spectral signature of at least three unsymmetric homochiral dimers. A comparison to signal-enhanced spectra of 1,2-ethanediol and to calculations uncovers at least three transiently homochiral dimer contributions as well. In few of these dimer structures, the intramolecular OHÁ Á ÁO contact present in monomeric 1,2-diols survives, despite the kinetic control in supersonic jet expansions. This provides further insights into the dimerisation mechanism of conformationally semi-flexible molecules in supersonic jets. Racemisation upon dimerisation is shown to be largely quenched under jet cooling conditions, whereas it should be strongly energy-driven at higher temperatures. The pronounced energetic preference for heterochiral aggregation of vicinal diols is also discussed in the context of chirality-induced spin selectivity. † Electronic supplementary information (ESI) available: Interactive and static structures, tables of experimental and computational details, energy diagrams for different levels of calculation, and additional experimental spectra. See

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“…[40] In other studies exploring the interactions of water and alcohols with ethers, changes in the preferred primary bonding, OÀH•••O versus OÀH•••p,w ere observed due to dispersion effects ands tructural flexibility. [41,42] The data presented here provideu seful experimental benchmarks forc omputationalm ethods, in particular for analysing and accurately describing the effects of dispersion and competing interactions. In this respect, B3LYP-D3BJ is emerginga s ar eliable cost-efficient method, whereas MP2 and M06-2X exhibit deficiencies that impact on their predictions of the structures and energetics of molecular systemsw ith severalw eak hydrogen bonds and dispersive interactions.…”

Section: Discussionmentioning

confidence: 99%

Binding Site Switch by Dispersion Interactions: Rotational Signatures of Fenchone–Phenol and Fenchone–Benzene Complexes

Burevschi

Alonso

Sanz

2020

Chemistry A European J

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Non‐covalent interactions between molecules determine molecular recognition and the outcome of chemical and biological processes. Characterising how non‐covalent interactions influence binding preferences is of crucial importance in advancing our understanding of these events. Here, we analyse the interactions involved in smell and specifically the effect of changing the balance between hydrogen‐bonding and dispersion interactions by examining the complexes of the common odorant fenchone with phenol and benzene, mimics of tyrosine and phenylalanine residues, respectively. Using rotational spectroscopy and quantum chemistry, two isomers of each complex have been identified. Our results show that the increased weight of dispersion interactions in these complexes changes the preferred binding site in fenchone and sets the basis for a better understanding of the effect of different residues in molecular recognition and binding events.

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Dispersion-controlled docking preference: multi-spectroscopic study on complexes of dibenzofuran with alcohols and water

Abstract: The planarity and rigidity of dibenzofuran inverts the docking preference for increasingly bulky R-OH solvent molecules, compared to the closely related diphenyl ether. Now, London dispersion favors OH⋯π hydrogen bonding.

Cited by 30 publications

References 81 publications

London Dispersion and Hydrogen‐Bonding Interactions in Bulky Molecules: The Case of Diadamantyl Ether Complexes

London Dispersion and Hydrogen‐Bonding Interactions in Bulky Molecules: The Case of Diadamantyl Ether Complexes

The reduced cohesion of homoconfigurational 1,2-diols

Binding Site Switch by Dispersion Interactions: Rotational Signatures of Fenchone–Phenol and Fenchone–Benzene Complexes

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