engleski

London dispersion and hydrogen bonding interactions in bulky molecules: The case of diadamantyl ether complexes

Diadamantyl ether (DAE, C20H30O) represents a good model to study the interplay between London dispersion and hydrogen bond interactions. Using broadband rotational spectroscopy, we report here an accurate experimental structure of the diadamantyl ether monomer and analyze its aggregates with water and a variety of aliphatic alcohols of increasing size. In the monomer, C–H···H–C London dispersion attractions between the two adamantyl subunits further stabilize its structure. Water and the alcohol partners bind to diadamantyl ether via hydrogen bonding and non‐covalent Owater/alcohol···H–CDAE and C–Halcohol···H–CDAE interactions. Electrostatic contributions drive the stabilization of all the complexes, whereas London dispersion interactions become more pronounced with increasing size of the alcohol. Complexes with dominant dispersion contributions are significantly higher in energy and were not observed in the experiment. The results presented herein shed light on the first steps of microsolvation and aggregation of molecular complexes with London dispersion energy donor (DED) groups and the kind of interactions that control them.

diadamantyl ether ; dispersion ; molecular complexes ; non-covalent interactions, quantum chemical calculations ; rotational spectroscopy

Humboldt Research Fellowship for Postdoctoral Researchers This work was financially supported by the Deutsche Forschungsgemeinschaft (SCHN1280/4-2, project number 271359857 and SCHR597/27-2)"Control of London dispersion interactions in molecular chemistry#