Charge‐Transfer Phase Transition of a Cyanide‐Bridged Fe<sup>II</sup>/Fe<sup>III</sup> Coordination Polymer

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  • Kuirun Zhang
    Institute for Materials Chemistry and Engineering Kyushu University 744 Motooka Nishi-ku Fukuoka 819-0395 Japan
  • Soonchul Kang
    Institute for Materials Chemistry and Engineering Kyushu University 744 Motooka Nishi-ku Fukuoka 819-0395 Japan
  • Zi‐shuo Yao
    Institute for Materials Chemistry and Engineering Kyushu University 744 Motooka Nishi-ku Fukuoka 819-0395 Japan
  • Kazusa Nakamura
    Institute for Materials Chemistry and Engineering Kyushu University 744 Motooka Nishi-ku Fukuoka 819-0395 Japan
  • Takashi Yamamoto
    Department of Chemistry Keio University 3-14-1 Hiyoshi Yokohama 223-8522 Japan
  • Yasuaki Einaga
    Department of Chemistry Keio University 3-14-1 Hiyoshi Yokohama 223-8522 Japan
  • Nobuaki Azuma
    Research Center for Structural Thermodynamics Graduate School of Science Osaka University Toyonaka Osaka 560-0043 Japan
  • Yuji Miyazaki
    Research Center for Structural Thermodynamics Graduate School of Science Osaka University Toyonaka Osaka 560-0043 Japan
  • Motohiro Nakano
    Research Center for Structural Thermodynamics Graduate School of Science Osaka University Toyonaka Osaka 560-0043 Japan
  • Shinji Kanegawa
    Institute for Materials Chemistry and Engineering Kyushu University 744 Motooka Nishi-ku Fukuoka 819-0395 Japan
  • Osamu Sato
    Institute for Materials Chemistry and Engineering Kyushu University 744 Motooka Nishi-ku Fukuoka 819-0395 Japan

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<jats:title>Abstract</jats:title><jats:p>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<jats:sup>II</jats:sup>/Fe<jats:sup>III</jats:sup> cyanide‐bridged coordination polymer, {[Fe(Tp)(CN)<jats:sub>3</jats:sub>]<jats:sub>2</jats:sub>Fe(bpe)⋅5 H<jats:sub>2</jats:sub>O}<jats:sub><jats:italic>n</jats:italic></jats:sub>, 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.</jats:p>

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