Binding of ion pairs and neutral guests by aryl-extended meso‑p-hydroxyphenyl calix[4]pyrrole : The interplay between three binding sites
Year of publication
2023
Authors
Pamuła, Małgorzata; Bulatov, Evgeny; Helttunen, Kaisa
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.
Show moreOrganizations and authors
Publication type
Publication format
Article
Parent publication type
Journal
Article type
Original article
Audience
ScientificPeer-reviewed
Peer-ReviewedMINEDU's publication type classification code
A1 Journal article (refereed), original researchPublication channel information
Journal
Publisher
Volume
1273
Issue
5
Article number
134268
ISSN
Publication forum
Publication forum level
1
Open access
Open access in the publisher’s service
Yes
Open access of publication channel
Partially open publication channel
Self-archived
Yes
Other information
Fields of science
Chemical sciences
Keywords
[object Object],[object Object],[object Object],[object Object],[object Object]
Publication country
Netherlands
Internationality of the publisher
International
Language
English
International co-publication
No
Co-publication with a company
No
DOI
10.1016/j.molstruc.2022.134268
The publication is included in the Ministry of Education and Culture’s Publication data collection
Yes