A1 Journal article (refereed)
Binding of ion pairs and neutral guests by aryl-extended meso‑p-hydroxyphenyl calix[4]pyrrole : The interplay between three binding sites (2023)

Pamuła, M., Bulatov, E., & Helttunen, K. (2023). Binding of ion pairs and neutral guests by aryl-extended meso‑p-hydroxyphenyl calix[4]pyrrole : The interplay between three binding sites. Journal of Molecular Structure, 1273(5), Article 134268. https://doi.org/10.1016/j.molstruc.2022.134268

JYU authors or editors

Publication details

All authors or editors: Pamuła, Małgorzata; Bulatov, Evgeny; Helttunen, Kaisa

Journal or series: Journal of Molecular Structure

ISSN: 0022-2860

eISSN: 1872-8014

Publication year: 2023

Publication date: 12/10/2022

Volume: 1273

Issue number: 5

Article number: 134268

Publisher: Elsevier BV

Publication country: Netherlands

Publication language: English

DOI: https://doi.org/10.1016/j.molstruc.2022.134268

Publication open access: Openly available

Publication channel open access: Partially open access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/83598

Abstract

An aryl-extended calix[4]pyrrole with four meso‑p-hydroxyphenyl substituents was investigated as a host for chloride, acetate, and benzoate anions. Crystal structures of pyridinium and imidazolium chloride complexes were obtained in which chloride ions are hydrogen bonded exo-cavity to the upper rim hydroxyl groups, and the aromatic cations are bound to the shallow cavity of the host. Furthermore, the calix[4]pyrrole formed a hydrogen bonded dimeric capsule templated by inclusion of adiponitrile guest in the endo-cavity binding site. NMR titrations revealed the preference of the OH groups of the host to bind anionic guests in solution. Benzoate anion had the highest binding constant (4 700 M−1) in acetonitrile. Density functional theory (DFT) calculations indicated that the exo-cavity complex with chloride anions was favoured by 23.2 kJ/mol over the endo-cavity complex, whereas the energies of endo- and exo-cavity benzoate complexes were of similar magnitude due to dispersion interactions between the host and the guest.

Keywords: anions; x-ray crystallography; molecules; interaction; supramolecular chemistry

Free keywords: anions; calix[4]pyrroles, host-guest systems; supramolecular chemistry; X-ray crystallography

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Ministry reporting: Yes

VIRTA submission year: 2023

JUFO rating: 1