Published in:Angewandte Chemie International Edition
Language:
English
DOI:
10.1002/anie.201801842
ISSN:
1433-7851;
1521-3773
Origination:
Footnote:
Description:
<jats:title>Abstract</jats:title><jats:p>Dispersion interactions can play an important role in understanding unusual binding behaviors. This is illustrated by a systematic study of the structural preferences of diphenyl ether (DPE)–alcohol aggregates, for which OH⋅⋅⋅O‐bound or OH⋅⋅⋅π‐bound isomers can be formed. The investigation was performed through a multi‐spectroscopic approach including IR/UV and microwave methods, combined with a detailed theoretical analysis. The resulting solvent‐size‐dependent trend for the structural preference turns out to be counter‐intuitive: the hydrogen‐bonded OH⋅⋅⋅O structures become more stable for larger alcohols, which are expected to be stronger dispersion energy donors and thus should prefer an OH⋅⋅⋅π arrangement. Dispersion interactions in combination with the twisting of the ether upon solvent aggregation are key for understanding this preference.</jats:p>