Jet FTIR spectroscopy of acetophenone–methanol balances reveals subtle solvation energy preferences by dispersion-tuning of the alkyl groups.

The influence of distant London dispersion forces on the docking preference of alcohols of different size between the two lone electron pairs of the carbonyl group in pinacolone was explored by infrared spectroscopy of the OH stretching fundamental in supersonic jet expansions of 1:1 solvate complexes. Experimentally, no pronounced tendency of the alcohol to switch from the methyl to the bulkier tert-butyl side with increasing size was found. In all cases, methyl docking dominates by at least a factor of two, whereas DFT-optimized structures suggest a very close balance for the larger alcohols, once corrected by CCSD(T) relative electronic energies. Together with inconsistencies when switching from a C4 to a C5 alcohol, this points at deficiencies of the investigated B3LYP and in particular TPSS functionals even after dispersion correction, which cannot be blamed on zero point energy effects. The search for density functionals which describe the harmonic frequency shift, the structural change and the energy difference between the docking isomers of larger alcohols to unsymmetric ketones in a satisfactory way is open.

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 that 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.

2-Butanone offers two hydrogen bond docking variants to a solvating methanol which are cleanly separated by supersonic jet infrared absorption spectroscopy in the OH-stretching range, resolving earlier action spectroscopy indeterminacies...

This work would not have been possible without the support of many people holding my hand through the struggles, especially my husband Joshua Zimmermann. Despite not having learned anything about chemistry since his school days, he listened to my explanations, problems and helped me through various disappointments. A special thanks also goes out to my friends and family, giving me a place to rest and regain my mental strength when needed.Most certainly it can be said that this work was only possible with the resilience and patience of Prof. Dr. Martin Suhm, always finding time to analyse and discuss projects or results and motivating me through various set backs or troubles. a Special thanks also go to my dedicated thesis committee members Prof. Dr.