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Direct Experimental Evidence for Halogen–Aryl π Interactions in Solution from Molecular Torsion Balances
Author(s) -
Sun Han,
Horatscheck André,
Martos Vera,
Bartetzko Max,
Uhrig Ulrike,
Lentz Dieter,
Schmieder Peter,
Nazaré Marc
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201700520
Subject(s) - halogen , aryl , torsion (gastropod) , chemistry , halogen bond , fluorine , computational chemistry , chemical physics , thermodynamics , organic chemistry , physics , alkyl , medicine , surgery
We dissected halogen–aryl π interactions experimentally using a bicyclic N‐arylimide based molecular torsion balances system, which is based on the influence of the non‐bonded interaction on the equilibria between folded and unfolded states. Through comparison of balances modulated by higher halogens with fluorine balances, we determined the magnitude of the halogen–aryl π interactions in our unimolecular systems to be larger than −5.0 kJ mol −1 , which is comparable with the magnitude estimated in the biomolecular systems. Our study provides direct experimental evidence of halogen–aryl π interactions in solution, which until now have only been revealed in the solid state and evaluated theoretically by quantum‐mechanical calculations.