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London Dispersion and Hydrogen‐Bonding Interactions in Bulky Molecules: The Case of Diadamantyl Ether Complexes
Author(s) -
Quesada Moreno María Mar,
Pinacho Pablo,
Pérez Cristóbal,
Šekutor Marina,
Schreiner Peter R.,
Schnell Melanie
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202001444
Subject(s) - hydrogen bond , ether , dispersion (optics) , monomer , london dispersion force , chemistry , molecule , alcohol , van der waals force , non covalent interactions , crystallography , computational chemistry , organic chemistry , polymer , physics , optics
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.