Charge‐Transfer Phase Transition of a Cyanide‐Bridged FeII/FeIII Coordination Polymer. Issue 20 (8th April 2016)

• Record Type: Journal Article
• Authors: Zhang, Kuirun; Kang, Soonchul; Yao, Zi‐shuo; Nakamura, Kazusa; Yamamoto, Takashi; Einaga, Yasuaki; Azuma, Nobuaki; Miyazaki, Yuji; Nakano, Motohiro; Kanegawa, Shinji; Sato, Osamu
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 20(2016)
• Page Start: 6047
• Page End: 6050
• Publication Date: 2016-04-08
• Subjects: charge transfer -- cyanide complexes -- iron -- mixed-valence -- phase transitions; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201601526
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Heterometallic Prussian blue analogues are known to exhibit thermally induced charge transfer, resulting in switching of optical and magnetic properties. However, charge‐transfer phase transitions have not been reported for the simplest FeFe cyanide‐bridged systems. A mixed‐valence Fe II /Fe III cyanide‐bridged coordination polymer, {[Fe(Tp)(CN)3 ]2 Fe(bpe)⋅5 H2 O} n, which demonstrates a thermally induced charge‐transfer phase transition, is described. As a result of the charge transfer during this phase transition, the high‐spin state of the whole system does not change to a low‐spin state. This result is in contrast to FeCo cyanide‐bridged systems that exhibit charge‐transfer‐induced spin transitions. Abstract : Feeling blue : A simple cyanide‐bridged Fe II /Fe III complex, inspired by Prussian blue (Fe III 4 [Fe II (CN)6 ]3 ⋅ x H2 O), displays switchable optical and magnetic properties upon metal‐to‐metal charge‐transfer phase transitions.