Through-Space Polar-π Interactions in 2,6-Diarylthiophenols

Jie Jian, Jordi Poater, Roel Hammink, Paul Tinnemans, Christine J. McKenzie, F. Matthias Bickelhaupt*, Jasmin Mecinović

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

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.

Original languageEnglish
Pages (from-to)1092-1100
Number of pages9
JournalChemPhysChem
Volume21
Issue number11
Early online date6 Apr 2020
DOIs
Publication statusPublished - 3 Jun 2020

Funding

J.J. acknowledges the financial support from the China Scholarship Council. F.M.B. acknowledges the Netherlands Organization for Scientific Research (NWO) for financial support. J.P. thanks the Spanish MINECO (CTQ2016‐77558‐R and MDM‐2017‐0767) and the Generalitat de Catalunya (2017SGR348). The Carlsberg Foundation is acknowledged for funding for the X‐ray diffractometer (grant CF15‐0675).

FundersFunder number
Netherlands Organization for Scientific Research
CarlsbergfondetCF15‐0675
Generalitat de Catalunya2017SGR348
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Ministerio de Economía y CompetitividadCTQ2016-77558-R, MDM-2017-0767
China Scholarship Council

    Keywords

    • aromatic compounds
    • molecular recognition
    • noncovalent interactions
    • polar-π interactions
    • thiols

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