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Self-assembly and properties of a discrete water-soluble Prussian blue analogue FeII/CoIII cube: confinement of a water molecule in aqueous solution Gonzálvez, Miguel A. Gallen Ortiz, Albert Ferrer García, Montserrat Martínez López, Manuel, 1957- Cobalt Compostos heterocíclics Lligands Cobalt Heterocyclic compounds Ligands Novel types of water-soluble anionic cubic cages, K4[{CoIII(Me3-Tacn)}4{FeII(CN)6}4] and Na4[{CoIII(Me3-Tacn)}4{FeII(CN)6}4] (Me3-Tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane), were prepared by means of a mechanistically designed self-assembly process between [Co(Me3-Tacn)Cl3] and A4[FeII(CN)6] (M = Na or K), consisting of a rate-limiting outer-sphere redox step, followed by a fast substitution/inner-sphere redox reaction sequence. These compounds show remarkable stability in aqueous solution at different pH ranges, displaying neat protonation processes and reversible oxidation with peroxodisulfate to its neutral {FeIII4CoIII4} form. Furthermore, the cages behave as a robust and water-soluble molecular Prussian Blue analogue capable of encapsulating {Na-OH2}+ pairs and K+ cations in aqueous solution, with the cubic structure of the complex being preserved. Substitution of the {Na-OH2}+ pairs by K+ is easily accomplished, and the electrochemical properties of the sodium and potassium salts of the new cages have been found to be dramatically dependent on the encapsulated units. 2020-05-25T16:09:25Z 2021-01-13T06:10:19Z 2020-01-13 2020-05-25T16:09:26Z info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Versió postprint del document publicat a: https://doi.org/10.1021/acs.inorgchem.9b03274 Inorganic Chemistry, 2020, vol. 59, num. 3, p. 1582-1587 https://doi.org/10.1021/acs.inorgchem.9b03274 (c) American Chemical Society , 2020 info:eu-repo/semantics/openAccess American Chemical Society Articles publicats en revistes (Química Inorgànica i Orgànica)