Details

Autor(en) / Beteiligte

• Wen, Wen
• Meng, Yin‐Shan
• Jiao, Cheng‐Qi
• Liu, Qiang
• Zhu, Hai‐Lang
• Li, Ya‐Ming
• Oshio, Hiroki
• Liu, Tao

Titel

A Mixed‐Valence {Fe13} Cluster Exhibiting Metal‐to‐Metal Charge‐Transfer‐Switched Spin Crossover

Ist Teil von

• Angewandte Chemie International Edition, 2020-09, Vol.59 (38), p.16393-16397

Auflage

International ed. in English

Ort / Verlag

Weinheim: Wiley Subscription Services, Inc

Erscheinungsjahr

2020

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• It is promising and challenging to manipulate the electronic structures and functions of materials utilizing both metal‐to‐metal charge transfer (MMCT) and spin‐crossover (SCO) to tune the valence and spin states of metal ions. Herein, a metallocyanate building block is used to link with a FeII‐triazole moiety and generates a mixed‐valence complex {[(Tp4‐Me)FeIII(CN)3]9[FeII4(trz‐ph)6]}⋅[Ph3PMe]2⋅[(Tp4‐Me)FeIII(CN)3] (1; trz‐ph=4‐phenyl‐4H‐1,2,4‐triazole). Moreover, MMCT occurs between FeIII and one of the FeII sites after heat treatment, resulting in the generation of a new phase, {[(Tp4‐Me)FeII(CN)3][(Tp4‐Me)FeIII(CN)3]8 [FeIIIFeII3(trz‐ph)6]}⋅ [Ph3PMe]2⋅[(Tp4‐Me)FeIII(CN)3] (1 a). Structural and magnetic studies reveal that MMCT can tune the two‐step SCO behavior of 1 into one‐step SCO behavior of 1 a. Our work demonstrates that the integration of MMCT and SCO can provide a new alternative for manipulating functional spin‐transition materials with accessible multi‐electronic states. Two step, one step: A mixed‐valence FeIII/FeII complex 1 was synthesized using [(Tp4‐Me)FeIII(CN)3]− to link with a FeII‐triazole moiety. Complex 1 underwent a metal‐to‐metal charge transfer (MMCT) between FeIII and one of the FeII sites after heat treatment, resulting in a new isostructural phase of 1 a. The MMCT can turn the two‐step spin crossover (SCO) behavior of 1 into one‐step SCO behavior of 1 a.