Carregant...
Fitxers
Tipus de document
ArticleVersió
Versió acceptadaData de publicació
Tots els drets reservats
Si us plau utilitzeu sempre aquest identificador per citar o enllaçar aquest document: https://hdl.handle.net/2445/183201
Molecular Approach to Alkali-Metal Encapsulation by a Prussian Blue Analogue FeII/CoIII Cube in Aqueous Solution: A Kineticomechanistic Exchange Study
Títol de la revista
Director/Tutor
ISSN de la revista
Títol del volum
Recurs relacionat
Resum
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.
Matèries
Matèries (anglès)
Citació
Citació
GONZÁLVEZ, Miguel a., BERNHARDT, Paul v., FONT BARDIA, Ma. mercedes, GALLEN ORTIZ, Albert, JOVER MODREGO, Jesús, FERRER GARCÍA, Montserrat, MARTÍNEZ LÓPEZ, Manuel. Molecular Approach to Alkali-Metal Encapsulation by a Prussian Blue Analogue FeII/CoIII Cube in Aqueous Solution: A Kineticomechanistic Exchange Study. _Inorganic Chemistry_. 2021. Vol. 60, núm. 18497-18422. [consulta: 24 de gener de 2026]. ISSN: 0020-1669. [Disponible a: https://hdl.handle.net/2445/183201]