2026-04-13T07:35:25Zhttps://recercat.cat/oai/request

oai:recercat.cat:2445/1623302025-12-04T21:40:36Zcom_2072_1057col_2072_478917col_2072_478933

00925njm 22002777a 4500 dc Gonzálvez, Miguel A. author Gallen Ortiz, Albert author Ferrer García, Montserrat author Martínez López, Manuel, 1957- author 2020-05-25T16:09:25Z 2021-01-13T06:10:19Z 2020-01-13 2020-05-25T16:09:26Z 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. Cobalt Compostos heterocíclics Lligands Cobalt Heterocyclic compounds Ligands Self-assembly and properties of a discrete water-soluble Prussian blue analogue FeII/CoIII cube: confinement of a water molecule in aqueous solution