Electron Transfer in the Cs⊂{Mn4Fe4} Cubic Switch: A Soluble Molecular Model of the MnFe Prussian‐Blue Analogues. (25th February 2020)

• Record Type: Journal Article
• Authors: Jiménez, Juan‐Ramón; Glatz, Jana; Benchohra, Amina; Gontard, Geoffrey; Chamoreau, Lise‐Marie; Meunier, Jean‐François; Bousseksou, Azzedine; Lescouëzec, Rodrigue
• Is Part Of: Angewandte Chemie. Volume 132:Number 21(2020)
• Page Start: 8166
• Page End: 8170
• Publication Date: 2020-02-25
• Subjects: Berliner-Blau-Analoga -- Elektrochromie -- Ladungstransfer -- Magnetismus -- Molekulare Schalter; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201916199
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: A mixed‐valence {Mn II 3 Mn III Fe II 2 Fe III 2 } cyanide‐bridged molecular cube hosting a caesium cation, Cs⊂{Mn4 Fe4 }, was synthesized and structurally characterized by X‐ray diffraction. Cyclic‐voltammetry measurements show that its electronic state can be switched between five different redox states, which results in a remarkable electrochromic effect. Magnetic measurements on fresh samples point to the occurrence of a spin‐state change near room temperature, which could be ascribed to a metal‐to‐metal electron transfer converting the {Fe II −CN−Mn III } pair into a {Fe III −CN−Mn II } pair. This feature was only previously observed in the polymeric MnFe Prussian‐blue analogues (PBAs). Moreover, this novel switchable molecule proved to be soluble and stable in organic solvents, paving the way for its integration into advanced materials. Abstract : Synthese ins Blaue : Der Cs⊂{Mn4 Fe4 }‐Würfel, das erste lösliche molekulare Modell der MnFe‐Analoga von Berliner Blau, wird mittels Röntgenbeugung, Cyclovoltammetrie, UV/Vis‐Absorptionsspektroskopie und magnetischer Messungen untersucht. Nahe Raumtemperatur findet ein Wechsel des Spinzustands statt, der einem Metall‐zu‐Metall‐Elektronentransfer zugeschrieben werden kann.