Cargando…
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...
Autores principales: | , , , , , , |
---|---|
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 |
_version_ | 1784624141309050880 |
---|---|
author | Gonzálvez, Miguel A. Bernhardt, Paul V. Font-Bardia, Mercè Gallen, Albert Jover, Jesús Ferrer, Montserrat Martínez, Manuel |
author_facet | Gonzálvez, Miguel A. Bernhardt, Paul V. Font-Bardia, Mercè Gallen, Albert Jover, Jesús Ferrer, Montserrat Martínez, Manuel |
author_sort | Gonzálvez, Miguel A. |
collection | PubMed |
description | [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. |
format | Online Article Text |
id | pubmed-8715505 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-87155052021-12-29 Molecular Approach to Alkali-Metal Encapsulation by a Prussian Blue Analogue Fe(II)/Co(III) Cube in Aqueous Solution: A Kineticomechanistic Exchange Study Gonzálvez, Miguel A. Bernhardt, Paul V. Font-Bardia, Mercè Gallen, Albert Jover, Jesús Ferrer, Montserrat Martínez, Manuel Inorg Chem [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. American Chemical Society 2021-11-12 2021-12-06 /pmc/articles/PMC8715505/ /pubmed/34766767 http://dx.doi.org/10.1021/acs.inorgchem.1c03001 Text en © 2021 American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Gonzálvez, Miguel A. Bernhardt, Paul V. Font-Bardia, Mercè Gallen, Albert Jover, Jesús Ferrer, Montserrat Martínez, Manuel Molecular Approach to Alkali-Metal Encapsulation by a Prussian Blue Analogue Fe(II)/Co(III) Cube in Aqueous Solution: A Kineticomechanistic Exchange Study |
title | Molecular Approach to Alkali-Metal Encapsulation by
a Prussian Blue Analogue Fe(II)/Co(III) Cube in
Aqueous Solution: A Kineticomechanistic Exchange Study |
title_full | Molecular Approach to Alkali-Metal Encapsulation by
a Prussian Blue Analogue Fe(II)/Co(III) Cube in
Aqueous Solution: A Kineticomechanistic Exchange Study |
title_fullStr | Molecular Approach to Alkali-Metal Encapsulation by
a Prussian Blue Analogue Fe(II)/Co(III) Cube in
Aqueous Solution: A Kineticomechanistic Exchange Study |
title_full_unstemmed | Molecular Approach to Alkali-Metal Encapsulation by
a Prussian Blue Analogue Fe(II)/Co(III) Cube in
Aqueous Solution: A Kineticomechanistic Exchange Study |
title_short | Molecular Approach to Alkali-Metal Encapsulation by
a Prussian Blue Analogue Fe(II)/Co(III) Cube in
Aqueous Solution: A Kineticomechanistic Exchange Study |
title_sort | molecular approach to alkali-metal encapsulation by
a prussian blue analogue fe(ii)/co(iii) cube in
aqueous solution: a kineticomechanistic exchange study |
url | 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 |
work_keys_str_mv | AT gonzalvezmiguela molecularapproachtoalkalimetalencapsulationbyaprussianblueanaloguefeiicoiiicubeinaqueoussolutionakineticomechanisticexchangestudy AT bernhardtpaulv molecularapproachtoalkalimetalencapsulationbyaprussianblueanaloguefeiicoiiicubeinaqueoussolutionakineticomechanisticexchangestudy AT fontbardiamerce molecularapproachtoalkalimetalencapsulationbyaprussianblueanaloguefeiicoiiicubeinaqueoussolutionakineticomechanisticexchangestudy AT gallenalbert molecularapproachtoalkalimetalencapsulationbyaprussianblueanaloguefeiicoiiicubeinaqueoussolutionakineticomechanisticexchangestudy AT joverjesus molecularapproachtoalkalimetalencapsulationbyaprussianblueanaloguefeiicoiiicubeinaqueoussolutionakineticomechanisticexchangestudy AT ferrermontserrat molecularapproachtoalkalimetalencapsulationbyaprussianblueanaloguefeiicoiiicubeinaqueoussolutionakineticomechanisticexchangestudy AT martinezmanuel molecularapproachtoalkalimetalencapsulationbyaprussianblueanaloguefeiicoiiicubeinaqueoussolutionakineticomechanisticexchangestudy |