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Tight and Selective Caging of Chloride Ions by a Pseudopeptidic Host
dc.contributor.author | Martí Vidal, Inés | |
dc.contributor.author | Bolte, Michael | |
dc.contributor.author | Burguete, M. Isabel | |
dc.contributor.author | Vicent Barrera, Cristian | |
dc.contributor.author | Alfonso Rodríguez, Ignacio | |
dc.contributor.author | Luis, Santiago V. | |
dc.date.accessioned | 2015-06-30T12:20:41Z | |
dc.date.available | 2015-06-30T12:20:41Z | |
dc.date.issued | 2014-06 | |
dc.identifier.issn | 0947-6539 | |
dc.identifier.issn | 1521-3765 | |
dc.identifier.uri | http://hdl.handle.net/10234/125415 | |
dc.description.abstract | The selective molecular recognition of chloride versus similar anions is a continuous challenge in supramolecular chemistry. We have designed and prepared a simple pseudopeptidic cage (1 a) that defines a cavity suitable for the tight encapsulation of chloride. The interaction of the protonated form of 1 a with different inorganic anions was studied in solution by 1H NMR spectroscopy and ESI-MS, and in the solid state by X-ray diffraction. The solution binding data showed that the association constants of 1 a to chloride are more than two orders of magnitude higher than to any other tested inorganic anion. Remarkably, 1 a displayed a high selectivity for chloride over other closely related halides such as bromide (selectivity=111), iodide (selectivity=719), and fluoride (selectivity >1000). Binding experiments (1H NMR spectroscopy and ESI-MS) suggested that 1 a has a high-affinity (inner) binding site and an additional low-affinity (external) binding site. The supramolecular complexes with F−, Cl−, and Br− have been also characterized by the X-ray diffraction of the corresponding [1 a⋅nHX] crystalline salts. The structural data show that the chloride anion is tightly encapsulated within the host, in a binding site defined by a very symmetric array of electrostatic H-bonds. For the fluoride salt, the size of the cage cavity is too large and is occupied by a water molecule, which fits inside the cage efficiently competing with F−. In the case of the bigger bromide, the mismatch of the anion inside the cage caused a geometrical distortion of the host and thus a large energetic penalty for the interaction. This minimalistic pseudopeptidic host represents a unique example of the construction of a simple well-defined binding pocket that allows the highly selective molecular recognition of a challenging substrate. | ca_CA |
dc.format.extent | 7 p. | ca_CA |
dc.format.mimetype | application/pdf | ca_CA |
dc.language.iso | eng | ca_CA |
dc.publisher | WILEY-VCH Verlag GmbH & Co. KGaA | ca_CA |
dc.relation.isPartOf | Chemistry - A European Journal Vol. 20, no. 24, 2014 | ca_CA |
dc.rights | © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim | ca_CA |
dc.rights.uri | http://rightsstatements.org/vocab/InC/1.0/ | * |
dc.subject | anions | ca_CA |
dc.subject | cage compounds | ca_CA |
dc.subject | molecular recognition | ca_CA |
dc.subject | pseudopeptides | ca_CA |
dc.subject | supramolecular chemistry | ca_CA |
dc.title | Tight and Selective Caging of Chloride Ions by a Pseudopeptidic Host | ca_CA |
dc.type | info:eu-repo/semantics/article | ca_CA |
dc.identifier.doi | http://dx.doi.org/10.1002/chem.201303604 | |
dc.rights.accessRights | info:eu-repo/semantics/restrictedAccess | ca_CA |
dc.relation.publisherVersion | http://onlinelibrary.wiley.com/doi/10.1002/chem.201303604/full | ca_CA |
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