Charge-Transfer Phase Transition of a Cyanide-Bridged FeII/FeIII Coordination Polymer

Kuirun Zhang; Soonchul Kang; Zi Shuo Yao; Kazusa Nakamura; Takashi Yamamoto; Yasuaki Einaga; Nobuaki Azuma; Yuji Miyazaki; Motohiro Nakano; Shinji Kanegawa; Osamu Sato

doi:10.1002/anie.201601526

Charge-Transfer Phase Transition of a Cyanide-Bridged Fe^II/Fe^III Coordination Polymer

Kuirun Zhang, Soonchul Kang, Zi Shuo Yao, Kazusa Nakamura, Takashi Yamamoto, Yasuaki Einaga, Nobuaki Azuma, Yuji Miyazaki, Motohiro Nakano, Shinji Kanegawa, Osamu Sato

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

49 Citations (Scopus)

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]₂Fe(bpe)5 H₂O}_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.

Original language	English
Pages (from-to)	6047-6050
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	55
Issue number	20
DOIs	https://doi.org/10.1002/anie.201601526
Publication status	Published - 2016 May 10

Keywords

charge transfer
cyanide complexes
iron
mixed-valence
phase transitions

ASJC Scopus subject areas

Catalysis
Chemistry(all)

Access to Document

10.1002/anie.201601526

Cite this

@article{d2aa915faf7146e083e5a32ae95de137,

title = "Charge-Transfer Phase Transition of a Cyanide-Bridged FeII/FeIII Coordination Polymer",

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 FeII/FeIII cyanide-bridged coordination polymer, {[Fe(Tp)(CN)3]2Fe(bpe)5 H2O}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.",

keywords = "charge transfer, cyanide complexes, iron, mixed-valence, phase transitions",

author = "Kuirun Zhang and Soonchul Kang and Yao, {Zi Shuo} and Kazusa Nakamura and Takashi Yamamoto and Yasuaki Einaga and Nobuaki Azuma and Yuji Miyazaki and Motohiro Nakano and Shinji Kanegawa and Osamu Sato",

note = "Funding Information: This work was supported by a JSPS KAKENHI Grant, numbers 26810039, 25288029, and 15H01018. This work was partly supported by Nanotechnology Platform Program (Molecule and Material Synthesis) of the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan. A part of this work was performed at the BL02B1 of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI; Proposal No. 2014B1471). Publisher Copyright: {\textcopyright} 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.",

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T1 - Charge-Transfer Phase Transition of a Cyanide-Bridged FeII/FeIII Coordination Polymer

AU - Zhang, Kuirun

AU - Kang, Soonchul

AU - Yao, Zi Shuo

AU - Nakamura, Kazusa

AU - Yamamoto, Takashi

AU - Einaga, Yasuaki

AU - Azuma, Nobuaki

AU - Miyazaki, Yuji

AU - Nakano, Motohiro

AU - Kanegawa, Shinji

AU - Sato, Osamu

N1 - Funding Information: This work was supported by a JSPS KAKENHI Grant, numbers 26810039, 25288029, and 15H01018. This work was partly supported by Nanotechnology Platform Program (Molecule and Material Synthesis) of the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan. A part of this work was performed at the BL02B1 of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI; Proposal No. 2014B1471). Publisher Copyright: © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

PY - 2016/5/10

Y1 - 2016/5/10

N2 - 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 FeII/FeIII cyanide-bridged coordination polymer, {[Fe(Tp)(CN)3]2Fe(bpe)5 H2O}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.

AB - 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 FeII/FeIII cyanide-bridged coordination polymer, {[Fe(Tp)(CN)3]2Fe(bpe)5 H2O}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.

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