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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
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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.
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GONZÁLVEZ, Miguel A., et al. Self-assembly and properties of a discrete water-soluble Prussian blue analogue FeII/CoIII cube: confinement of a water molecule in aqueous solution. Inorganic Chemistry. 2020. Vol. 59, num. 3, pags. 1582-1587. ISSN 0020-1669. [consulted: 11 of October of 2026]. Available at: https://hdl.handle.net/2445/162330