Please use this identifier to cite or link to this item:
http://hdl.handle.net/2445/183201
Title: | Molecular Approach to Alkali-Metal Encapsulation by a Prussian Blue Analogue FeII/CoIII Cube in Aqueous Solution: A Kineticomechanistic Exchange Study |
Author: | Gonzálvez, Miguel A. Bernhardt, Paul V. Font Bardia, Ma. Mercedes Gallen Ortiz, Albert Jover Modrego, Jesús Ferrer García, Montserrat Martínez López, Manuel, 1957- |
Keywords: | Complexos metàl·lics Lligands Metalls alcalins Metal complexes Ligands Alkali metals |
Issue Date: | 6-Dec-2021 |
Publisher: | American Chemical Society |
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. |
Note: | Versió postprint del document publicat a: https://doi.org/10.1021/acs.inorgchem.1c03001 |
It is part of: | Inorganic Chemistry, 2021, vol. 60, p. 18497-18422 |
URI: | http://hdl.handle.net/2445/183201 |
Related resource: | https://doi.org/10.1021/acs.inorgchem.1c03001 |
ISSN: | 0020-1669 |
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) |
Files in This Item:
File | Description | Size | Format | |
---|---|---|---|---|
716283.pdf | 1.8 MB | Adobe PDF | View/Open |
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.