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 language | English |
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Pages (from-to) | 6087-6096 |
Number of pages | 10 |
Journal | Journal of Organic Chemistry |
Volume | 87 |
Issue number | 9 |
Early online date | 26 Apr 2022 |
DOIs | |
Publication status | Published - 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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CCDC 2144633: Experimental Crystal Structure Determination
McKenzie, C. J. (Contributor), Mecinović, J. (Contributor), Hammink, R. (Contributor), Poater, J. (Contributor), Tinnemans, P. (Contributor), Bickelhaupt, M. (Contributor) & Jian, J. (Contributor), The Cambridge Structural Database, 1 Jan 2022
DOI: 10.5517/ccdc.csd.cc29znqp, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc29znqp&sid=DataCite
Dataset / Software: Dataset
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CCDC 2144635: Experimental Crystal Structure Determination
Poater, J. (Contributor), Mecinović, J. (Contributor), Tinnemans, P. (Contributor), Bickelhaupt, M. (Contributor), Jian, J. (Contributor), McKenzie, C. J. (Contributor) & Hammink, R. (Contributor), The Cambridge Structural Database, 1 Jan 2022
DOI: 10.5517/ccdc.csd.cc29znsr, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc29znsr&sid=DataCite
Dataset / Software: Dataset
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CCDC 2144634: Experimental Crystal Structure Determination
Mecinović, J. (Contributor), Poater, J. (Contributor), Jian, J. (Contributor), Hammink, R. (Contributor), McKenzie, C. J. (Contributor), Bickelhaupt, M. (Contributor) & Tinnemans, P. (Contributor), The Cambridge Structural Database, 1 Jan 2022
DOI: 10.5517/ccdc.csd.cc29znrq, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc29znrq&sid=DataCite
Dataset / Software: Dataset