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http://hdl.handle.net/10773/35854
Title: | Being positive is not everything: experimental and computational studies on the selectivity of a self-assembled, multiple redox-state receptor that binds anions with up to picomolar affinities |
Author: | Zubi, Ahmed Alnafisah, Hawazin A. Turega, Simon Marques, Igor Gomes, José R. B. Thomas, Jim A. Félix, Vítor |
Keywords: | Binding Sites Hydrogen Bonding Oxidation-Reduction Anions |
Issue Date: | 24-Jan-2022 |
Publisher: | Wiley-Blackwell |
Abstract: | The interaction of the self-assembled trinuclear ruthenium bowl 13+ , that displays three other accessible oxidation states, with oxo-anions is investigated. Using a combination of NMR and electrochemical experimental data, estimates of the binding affinities of 14+ , 15+ , and 16+ for both halide and oxo-anions were derived. This analysis revealed that, across the range of oxidation states of the host, both high anion binding affinities (>109 M-1 for specific guests bound to 16+ ) and high selectivities (a range of >107 M-1 ) were observed. As the crystal structure of binding of the hexafluorophosphate anion revealed that the host has two potential binding sites (named the α and β pockets), the host-guest properties of both putative binding sites of the bowl, in all of its four oxidation states, were investigated through detailed quantum-based computational studies. These studies revealed that, due to the interplay of ion-ion interactions, charge-assisted hydrogen-bonding and anion-π interactions, binding to the α pocket is generally preferred, except for the case of the relatively large and lipophilic hexafluorophosphate anionic guest and the host in the highest oxidation states, where the β pocket becomes relatively favourable. This analysis confirms that host-guest interactions involving structurally complex supramolecular architectures are driven by a combination of non-covalent interactions and, even in the case of charged binding pairs, simple ion-ion interactions alone cannot accurately define these recognition processes. |
Peer review: | yes |
URI: | http://hdl.handle.net/10773/35854 |
DOI: | 10.1002/chem.202102465 |
ISSN: | 0947-6539 |
Publisher Version: | https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202102465 |
Appears in Collections: | CICECO - Artigos DQ - Artigos |
Files in This Item:
File | Description | Size | Format | |
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Anions_author_version.pdf | Author's version | 962.44 kB | Adobe PDF | View/Open |
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