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Main Title: Microhydration Structures of Protonated Oxazole
Author(s): Chatterjee, Kuntal
Dopfer, Otto
Type: Article
Language Code: en
Abstract: The initial microhydration structures of the protonated pharmaceutical building block oxazole (Ox), H+Ox-Wn≤4, are determined by infrared photodissociation (IRPD) spectroscopy combined with quantum chemical dispersion-corrected density functional theory calculations (B3LYP-D3/aug-cc-pVTZ). Protonation of Ox, achieved by chemical ionization in a H2-containing plasma, occurs at the most basic N atom. The analysis of systematic shifts of the NH and OH stretch vibrations as a function of the cluster size provides a clear picture for the preferred cluster growth in H+Ox-Wn. For n = 1–3, the IRPD spectra are dominated by a single isomer, and microhydration of H+Ox with hydrophilic protic W ligands occurs by attachment of a hydrogen-bonded (H-bonded) Wn solvent cluster to the acidic NH group via an NH···O H-bond. Such H-bonded networks are stabilized by strong cooperativity effects. This is in contrast to previously studied hydrophobic ligands, which prefer interior ion solvation. The strength of the NH···O ionic H-bond increases with the degree of hydration because of the increasing proton affinity (PA) of the Wn cluster. At n = 4, proton-transferred structures of the type Ox-H+Wn become energetically competitive with H+Ox-Wn structures, because differences in solvation energies can compensate for the differences in the PAs, and barrierless proton transfer from H+Ox to the Wn solvent subcluster becomes feasible. Indeed, the IRPD spectrum of the n = 4 cluster is more complex suggesting the presence of more than one isomer, although it lacks unequivocal evidence for the predicted intracluster proton transfer.
Issue Date: 22-Aug-2019
Date Available: 28-Aug-2019
DDC Class: 541 Physikalische Chemie
Subject(s): ligands
structural change
aromatic molecule
Journal Title: The Journal of Physical Chemistry A
Publisher: American Chemical Society
Publisher Place: Washington DC
Publisher DOI: 10.1021/acs.jpca.9b06587
EISSN: 1520-5215
ISSN: 1089-5639
Appears in Collections:FG Lasermolekülspektroskopie und Umweltphysik » Publications

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