Please use this identifier to cite or link to this item: http://dx.doi.org/10.14279/depositonce-8834
Main Title: Unraveling the protonation site of oxazole and solvation with hydrophobic ligands by infrared photodissociation spectroscopy
Author(s): Chatterjee, Kuntal
Dopfer, Otto
Type: Article
Language Code: en
Abstract: Protonation and solvation of heterocyclic aromatic building blocks control the structure and function of many biological macromolecules. Herein the infrared photodissociation (IRPD) spectra of protonated oxazole (H+Ox) microsolvated by nonpolar and quadrupolar ligands, H+Ox-Ln with L = Ar (n = 1–2) and L = N2 (n = 1–4), are analyzed by density functional theory calculations at the dispersion-corrected B3LYP-D3/aug-cc-pVTZ level to determine the preferred protonation and ligand binding sites. Cold H+Ox-Ln clusters are generated in an electron impact cluster ion source. Protonation of Ox occurs exclusively at the N atom of the heterocyclic ring, in agreement with the thermochemical predictions. The analysis of the systematic shifts of the NH stretch frequency in the IRPD spectra of H+Ox-Ln provides a clear picture of the sequential cluster growth and the type and strength of various competing ligand binding motifs. The most stable structures observed for the H+Ox-L dimers (n = 1) exhibit a linear NH⋯L hydrogen bond (H-bond), while π-bonded isomers with L attached to the aromatic ring are local minima on the potential and thus occur at a lower abundance. From the spectra of the H+Ox-L(π) isomers, the free NH frequency of bare H+Ox is extrapolated as νNH = 3444 ± 3 cm−1. The observed H+Ox-L2 clusters with L = N2 feature both bifurcated NH⋯L2 (2H isomer) and linear NH⋯L H-bonding motifs (H/π isomer), while for L = Ar only the linear H-bond is observed. No H+Ox-L2(2π) isomers are detected, confirming that H-bonding to the NH group is more stable than π-bonding to the ring. The most stable H+Ox-(N2)n clusters with n = 3–4 have 2H/(n − 2)π structures, in which the stable 2H core ion is further solvated by (n − 2) π-bonded ligands. Upon N-protonation, the aromatic C–H bonds of the Ox ring get slightly stronger, as revealed by higher CH stretch frequencies and strongly increased IR intensities.
URI: https://depositonce.tu-berlin.de/handle/11303/9812
http://dx.doi.org/10.14279/depositonce-8834
Issue Date: 19-Jan-2019
Date Available: 19-Aug-2019
DDC Class: 540 Chemie und zugeordnete Wissenschaften
Subject(s): heterocyclic aromatic building block
nonpolar ligand
quadrupolar ligand
IRPD
License: https://creativecommons.org/licenses/by/3.0/
Journal Title: Physical Chemistry Chemical Physics
Publisher: Royal Society of Chemistry
Publisher Place: London
Volume: 21
Issue: 27
Publisher DOI: 10.1039/C9CP02787D
Page Start: 15157
Page End: 15166
EISSN: 1463-9084
ISSN: 1463-9076
Appears in Collections:FG Lasermolekülspektroskopie und Umweltphysik » Publications

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