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Substituent Effects on Edge‐to‐Face Aromatic Interactions
Author(s) -
Carver Fiona J.,
Hunter Christopher A.,
Livingstone David J.,
McCabe James F.,
Seward Eileen M.
Publication year - 2002
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 - 10.1002/1521-3765(20020703)8:13<2847::aid-chem2847>3.0.co;2-m
Subject(s) - substituent , chemistry , ring (chemistry) , aromaticity , dipole , computational chemistry , electrostatics , crystallography , stereochemistry , molecule , organic chemistry
Chemical double mutant cycles have been used to measure the magnitude of edge‐to‐face aromatic interactions in hydrogen‐bonded zipper complexes as a function of substituents on both aromatic rings. The interaction energies vary depending on the combination of substituents from +1.0 kJ mol −1 (repulsive), to −4.9 kJ mol −1 (attractive). The results correlate with the Hammett substituent constants which indicates that electrostatic interactions are responsible for the observed differences in interaction energy. The experiments can be rationalised based on local electrostatic interactions between the protons on the edge ring and the π‐electron density on the face ring as well as global electrostatic interactions between the overall dipoles on the two aromatic groups.