title: Redox-Assisted Self-Assembly of a Water-Soluble Cyanido-Bridged Mixed Valence {CoIII/FeII}2Square.
abstract: The facile redox-assisted assembly of a water-soluble, extremely robust, cyanide-bridged mixed-valence [{CoIII{(Me)2(μ-ET)cyclen}}2{(μ-NC)2FeII(CN)4}2]2-square is reported. The preparation process involved the use of the enhanced lability of inert CoIIIsynthons triggered by outer-sphere redox processes. Characterization of the final compounds has been carried out by NMR, UV/Vis, electrochemistry, and ICP analyses. DFT calculations have been conducted to optimize a structure that has the same hydrodynamic radius as that obtained from DOSY experiments. The new compound is extremely robust, surviving in aqueous solution within the 0-12 pH range for months. The species shows a high affinity for both protons and hydroxo ions in aqueous medium.
authors.affiliation: Departament de Química Inorgànica i Orgànica, Secció de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1-11, 08028, Barcelona, Spain.
authors.forename: Laura
authors.initials: L
authors.lastname: Alcázar
authors.affiliation: Departament de Química Inorgànica i Orgànica, Secció de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1-11, 08028, Barcelona, Spain.
authors.forename: Gabriel
authors.identifier: http://orcid.org/0000-0001-7519-4522
authors.initials: G
authors.lastname: Aullón
authors.affiliation: Departament de Química Inorgànica i Orgànica, Secció de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1-11, 08028, Barcelona, Spain.
authors.forename: Montserrat
authors.identifier: http://orcid.org/0000-0002-4034-2596
authors.initials: M
authors.lastname: Ferrer
authors.affiliation: Departament de Química Inorgànica i Orgànica, Secció de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1-11, 08028, Barcelona, Spain. manel-martinez@qi.ub.es.
authors.forename: Manuel
authors.identifier: http://orcid.org/0000-0002-6289-4586
authors.initials: M
authors.lastname: Martínez
keywords: cyanido bridged species; mixed-valence complexes; redox mechanisms; self-assembly