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Inter‐ and Intramolecular Aryl–Aryl Interactions in Partially Fluorinated Ethylenedioxy‐bridged Bisarenes **
Author(s) -
Weddeling JanHenrik,
Vishnevskiy Yury V.,
Neumann Beate,
Stammler HansGeorg,
Mitzel Norbert W.
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.202003259
Subject(s) - intramolecular force , aryl , intermolecular force , chemistry , molecule , ethylenedioxy , crystallography , conformational isomerism , london dispersion force , computational chemistry , stereochemistry , van der waals force , organic chemistry , alkyl
Several ethylenedioxy‐bridged bisarenes with a variety of type and number of aryl groups were synthesized to study non‐covalent dispersion‐driven inter‐ and intramolecular aryl–aryl interactions in the solid state and gas phase. Intramolecular interactions are preferably found in the gas phase. DFT calculations with and without dispersion correction show larger interacting aromatic groups increase the stabilization energy of folded conformers and decrease the intermolecular centroid–centroid distance. Single‐molecule structures generally adopt folded conformations with short intramolecular aryl–aryl contacts. Gas electron diffraction experiments were performed exemplarily for 1‐(pentafluorophenoxy)‐2‐(phenoxy)ethane. A new procedure for structure refinement was developed to deal with the conformational complexity of such molecules. The results are an experimental confirmation of the existence of folded conformations of this molecule with short intramolecular aryl–aryl distances in the gas phase. Solid‐state structures are dominated by stretched structures without intramolecular aryl–aryl interactions but interactions with neighboring molecules.