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http://hdl.handle.net/2445/183201
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DC Field | Value | Language |
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dc.contributor.author | Gonzálvez, Miguel A. | - |
dc.contributor.author | Bernhardt, Paul V. | - |
dc.contributor.author | Font Bardia, Ma. Mercedes | - |
dc.contributor.author | Gallen Ortiz, Albert | - |
dc.contributor.author | Jover Modrego, Jesús | - |
dc.contributor.author | Ferrer García, Montserrat | - |
dc.contributor.author | Martínez López, Manuel, 1957- | - |
dc.date.accessioned | 2022-02-15T23:07:48Z | - |
dc.date.available | 2022-12-06T06:10:21Z | - |
dc.date.issued | 2021-12-06 | - |
dc.identifier.issn | 0020-1669 | - |
dc.identifier.uri | http://hdl.handle.net/2445/183201 | - |
dc.description.abstract | The preparation of a series of alkali-metal inclusion complexes of the molecular cube [{CoIII(Me3-tacn)}4{FeII(CN)6}4]4- (Me3-tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane), a mixed-valent Prussian Blue analogue bearing bridging cyanido ligands, has been achieved by following a redox-triggered self-assembly process. The molecular cubes are extremely robust and soluble in aqueous media ranging from 5 M [H+] to 2 M [OH-]. All the complexes have been characterized by the standard mass spectometry, UV-vis, inductively coupled plasma, multinuclear NMR spectroscopy, and electrochemistry. Furthermore, X-ray diffraction analysis of the sodium and lithium salts has also been achieved, and the inclusion of moieties of the form {M-OH2}+ (M = Li, Na) is confirmed. These inclusion complexes in aqueous solution are rather inert to cation exchange and are characterized by a significant decrease in acidity of the confined water molecule due to hydrogen bonding inside the cubic cage. Exchange of the encapsulated cationic {M-OH2}+ or M+ units by other alkali metals has also been studied from a kineticomechanistic perspective at different concentrations, temperatures, ionic strengths, and pressures. In all cases, the thermal and pressure activation parameters obtained agree with a process that is dominated by differences in hydration of the cations entering and exiting the cage, although the size of the portal enabling the exchange also plays a determinant role, thus not allowing the large Cs+ cation to enter. All the exchange substitutions studied follow a thermodynamic sequence that relates with the size and polarizing capability of the different alkali cations; even so, the process can be reversed, allowing the entry of {Li-OH2}+ units upon adsorption of the cube on an anion exchange resin and subsequent washing with a Li+ solution. | - |
dc.format.extent | -74 p. | - |
dc.format.mimetype | application/pdf | - |
dc.language.iso | eng | - |
dc.publisher | American Chemical Society | - |
dc.relation.isformatof | Versió postprint del document publicat a: https://doi.org/10.1021/acs.inorgchem.1c03001 | - |
dc.relation.ispartof | Inorganic Chemistry, 2021, vol. 60, p. 18497-18422 | - |
dc.relation.uri | https://doi.org/10.1021/acs.inorgchem.1c03001 | - |
dc.rights | (c) American Chemical Society , 2021 | - |
dc.source | Articles publicats en revistes (Química Inorgànica i Orgànica) | - |
dc.subject.classification | Complexos metàl·lics | - |
dc.subject.classification | Lligands | - |
dc.subject.classification | Metalls alcalins | - |
dc.subject.other | Metal complexes | - |
dc.subject.other | Ligands | - |
dc.subject.other | Alkali metals | - |
dc.title | Molecular Approach to Alkali-Metal Encapsulation by a Prussian Blue Analogue FeII/CoIII Cube in Aqueous Solution: A Kineticomechanistic Exchange Study | - |
dc.type | info:eu-repo/semantics/article | - |
dc.type | info:eu-repo/semantics/acceptedVersion | - |
dc.identifier.idgrec | 716283 | - |
dc.date.updated | 2022-02-15T23:07:48Z | - |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | - |
Appears in Collections: | Articles publicats en revistes (Institut de Nanociència i Nanotecnologia (IN2UB)) Articles publicats en revistes (Institut de Química Teòrica i Computacional (IQTCUB)) Articles publicats en revistes (Química Inorgànica i Orgànica) |
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File | Description | Size | Format | |
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716283.pdf | 1.8 MB | Adobe PDF | View/Open |
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