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Through-Space Polar-π Interactions in 2,6-Diarylthiophenols |
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| Authors: | Jie Jian Dr. Jordi Poater Dr. Roel Hammink Dr. Paul Tinnemans Prof. Dr. Christine J. McKenzie Prof. Dr. F. Matthias Bickelhaupt Prof. Dr. Jasmin Mecinović |
| Affiliation: | 1. Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, 5230 Odense, Denmark These authors contributed equally to this work.;2. ICREA, Passeig Lluís Companys 23, 08010 Barcelona, Spain;3. Division of Immunotherapy, Oncode Institute, Radboud University Medical Center, Nijmegen, The Netherlands;4. Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands;5. Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, 5230 Odense, Denmark |
| Abstract: | Molecular recognition between polar groups and aromatic molecules is fundamentally important to rational drug design. Although it has been well established that many polar functionalities interact with electron-rich aromatic residues through energetically favorable polar-π interactions, there is a limited understanding of the association between thiols and aromatic systems. Herein we report physical-organic chemistry studies on 2,6-diarylthiophenols that possess the central thiophenol ring and two flanking aromatic rings with tunable electronic properties caused by substituents at distant para position. Hammett analysis revealed that pKa values and proton affinities correlate well with Hammett sigma values of substituents. Additional energy decomposition analysis supported the conclusion that both through-space SH-π interactions and S−-π interactions contribute to intramolecular stabilization of 2,6-diarylthiophenols. |
| Keywords: | aromatic compounds molecular recognition noncovalent interactions polar-π interactions thiols |