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Molecular Approach to Alkali-Metal Encapsulation by a Prussian Blue Analogue Fe(II)/Co(III) Cube in Aqueous Solution: A Kineticomechanistic Exchange Study

[Image: see text] The preparation of a series of alkali-metal inclusion complexes of the molecular cube [{Co(III)(Me(3)-tacn)}(4){Fe(II)(CN)(6)}(4)](4–) (Me(3)-tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane), a mixed-valent Prussian Blue analogue bearing bridging cyanido ligands, has been achieved b...

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Detalles Bibliográficos
Autores principales: Gonzálvez, Miguel A., Bernhardt, Paul V., Font-Bardia, Mercè, Gallen, Albert, Jover, Jesús, Ferrer, Montserrat, Martínez, Manuel
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8715505/
https://www.ncbi.nlm.nih.gov/pubmed/34766767
http://dx.doi.org/10.1021/acs.inorgchem.1c03001
Descripción
Sumario:[Image: see text] The preparation of a series of alkali-metal inclusion complexes of the molecular cube [{Co(III)(Me(3)-tacn)}(4){Fe(II)(CN)(6)}(4)](4–) (Me(3)-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–OH(2)}(+) (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–OH(2)}(+) 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–OH(2)}(+) units upon adsorption of the cube on an anion exchange resin and subsequent washing with a Li(+) solution.