Preprint Article Version 1 Preserved in Portico This version is not peer-reviewed

Halogens in Acetophenones Direct the Hydrogen Bond Docking Preference of Phenol via Stacking Interactions

Version 1 : Received: 19 July 2021 / Approved: 20 July 2021 / Online: 20 July 2021 (16:06:47 CEST)

How to cite: Zimmermann, C.; Lange, M.; Suhm, M.A. Halogens in Acetophenones Direct the Hydrogen Bond Docking Preference of Phenol via Stacking Interactions. Preprints 2021, 2021070462 (doi: 10.20944/preprints202107.0462.v1). Zimmermann, C.; Lange, M.; Suhm, M.A. Halogens in Acetophenones Direct the Hydrogen Bond Docking Preference of Phenol via Stacking Interactions. Preprints 2021, 2021070462 (doi: 10.20944/preprints202107.0462.v1).

Abstract

Phenol is added to acetophenone (methyl phenyl ketone) and to six of its halogenated derivatives in a supersonic jet expansion to determine the hydrogen bonding preference of the cold and isolated 1:1 complexes by linear infrared spectroscopy. Halogenation is found to have a pronounced effect on the docking site in this intermolecular ketone balance experiment. The spectra unambiguously decide between competing variants of phenyl group stacking due to their differences in hydrogen bond strength. Structures where the phenyl group interaction strongly distorts the hydrogen bond are more difficult to quantify in the experiment. For unsubstituted acetophenone, phenol clearly prefers the methyl side despite a predicted sub-kJ/mol advantage which is nearly independent of zero point vibrational energy, turning this complex into a challenging benchmark system for electronic structure methods which include long range dispersion interactions in some way.

Subject Areas

London dispersion; ketone complexes; density functional theory; hydrogen bonds; molecular recognition; vibrational spectroscopy; gas phase; benchmark

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