Probing Noncovalent Interactions in [3,3]Metaparacyclophanes

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

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

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Abstract

Arene-arene interactions are fundamentally important in molecular recognition. To precisely probe arene-arene interactions in cyclophanes, we designed and synthesized (2,6-phenol)paracyclophanes and (2,6-aniline)paracyclophanes that possess two aromatic rings in close proximity. Fine-tuning the aromatic character of one aromatic ring by fluorine substituents enables investigations on the intramolecular interactions between the electron-rich phenol and aniline with tetra-H- and tetra-F-substituted benzene. pKa measurements revealed that the tetra-F-template increases the acidity of the phenol (ΔpKa = 0.55). X-ray crystallography and computational analyses demonstrated that all [3,3]metaparacyclophanes adopt cofacial parallel conformations, implying the presence of π-πstacking interactions. Advanced quantum chemical analyses furthermore revealed that both electrostatic interactions and orbital interactions provide the key contribution to the structure and stability of [3,3]metaparacyclophanes.

Original languageEnglish
Pages (from-to)6087-6096
Number of pages10
JournalJournal of Organic Chemistry
Volume87
Issue number9
Early online date26 Apr 2022
DOIs
Publication statusPublished - 6 May 2022

Bibliographical note

Funding Information:
J.J. thanks the China Scholarship Council (CSC201808440511). We thank the Netherlands Organization for Scientific Research (NWO) for financial support. J.P. thanks the Spanish MINECO (PID2019-106830GB-I00 and MDM-2017-0767).

Publisher Copyright:
© 2022 American Chemical Society.

Funding

J.J. thanks the China Scholarship Council (CSC201808440511). We thank the Netherlands Organization for Scientific Research (NWO) for financial support. J.P. thanks the Spanish MINECO (PID2019-106830GB-I00 and MDM-2017-0767).

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