London Dispersion and Hydrogen‐Bonding Interactions in Bulky Molecules: The Case of Diadamantyl Ether Complexes

Diadamantyl ether (DAE, C(20)H(30)O) represents a good model to study the interplay between London dispersion and hydrogen‐bond interactions. By using broadband rotational spectroscopy, an accurate experimental structure of the diadamantyl ether monomer is obtained and its aggregates with water and a variety of aliphatic alcohols of increasing size are analyzed. 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 through hydrogen bonding and non‐covalent O(water/alcohol)⋅⋅⋅H−C(DAE) and C−H(alcohol)⋅⋅⋅H−C(DAE) 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.