TY - JOUR
T1 - Three-Step Spin State Transition and Hysteretic Proton Transfer in the Crystal of an Iron(II) Hydrazone Complex
AU - Nakanishi, Takumi
AU - Hori, Yuta
AU - Wu, Shuqi
AU - Sato, Hiroyasu
AU - Okazawa, Atsushi
AU - Kojima, Norimichi
AU - Horie, Yusuke
AU - Okajima, Hajime
AU - Sakamoto, Akira
AU - Shiota, Yoshihito
AU - Yoshizawa, Kazunari
AU - Sato, Osamu
N1 - Funding Information:
We thank for the support by MEXT KAKENHI (Grant Numbers JP19K15524, JP17H01197, JP16H00849, JP17K05761, JP24109014, JP15K13710, JP17H03117, JP16K05421 and JP17H06928, JP20K15247), by the MEXT Project of “Integrated Research Consortium on Chemical Sciences”, “Elements Strategy Initiative to Form Core Research Center”, JST‐CREST “Innovative Catalysts” JPMJCR15P5, and by the Cooperative Research Program of “Network Joint Research Center for Materials and Devices”. The synchrotron radiation experiments were performed at the BL02B1 of SPring‐8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal No. 2017A1364, 2017B1285, 2018A1213, 2018B1259 and 2019B1272). This work was partly supported by Nanotechnology Platform Program (Molecule and Material Synthesis) of MEXT, Japan. The computation was carried out using the computer facilities at Research Institute for Information Technology, Kyushu University.
Funding Information:
We thank for the support by MEXT KAKENHI (Grant Numbers JP19K15524, JP17H01197, JP16H00849, JP17K05761, JP24109014, JP15K13710, JP17H03117, JP16K05421 and JP17H06928, JP20K15247), by the MEXT Project of “Integrated Research Consortium on Chemical Sciences”, “Elements Strategy Initiative to Form Core Research Center”, JST-CREST “Innovative Catalysts” JPMJCR15P5, and by the Cooperative Research Program of “Network Joint Research Center for Materials and Devices”. The synchrotron radiation experiments were performed at the BL02B1 of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal No. 2017A1364, 2017B1285, 2018A1213, 2018B1259 and 2019B1272). This work was partly supported by Nanotechnology Platform Program (Molecule and Material Synthesis) of MEXT, Japan. The computation was carried out using the computer facilities at Research Institute for Information Technology, Kyushu University.
Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2020/8/24
Y1 - 2020/8/24
N2 - A proton–electron coupling system, exhibiting unique bistability or multistability of the protonated state, is an attractive target for developing new switchable materials based on proton dynamics. Herein, we present an iron(II) hydrazone crystalline compound, which displays the stepwise transition and bistability of proton transfer at the crystal level. These phenomena are realized through the coupling with spin transition. Although the multi-step transition with hysteresis has been observed in various systems, the corresponding behavior of proton transfer has not been reported in crystalline systems; thus, the described iron(II) complex is the first example. Furthermore, because proton transfer occurs only in one of the two ligands and π electrons redistribute in it, the dipole moment of the iron(II) complexes changes with the proton transfer, wherein the total dipole moment in the crystal was canceled out owing to the antiferroelectric-like arrangement.
AB - A proton–electron coupling system, exhibiting unique bistability or multistability of the protonated state, is an attractive target for developing new switchable materials based on proton dynamics. Herein, we present an iron(II) hydrazone crystalline compound, which displays the stepwise transition and bistability of proton transfer at the crystal level. These phenomena are realized through the coupling with spin transition. Although the multi-step transition with hysteresis has been observed in various systems, the corresponding behavior of proton transfer has not been reported in crystalline systems; thus, the described iron(II) complex is the first example. Furthermore, because proton transfer occurs only in one of the two ligands and π electrons redistribute in it, the dipole moment of the iron(II) complexes changes with the proton transfer, wherein the total dipole moment in the crystal was canceled out owing to the antiferroelectric-like arrangement.
KW - hydrazone complexes
KW - proton transfer
KW - solid-state chemistry
KW - spin crossover
KW - switchable materials
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U2 - 10.1002/anie.202006763
DO - 10.1002/anie.202006763
M3 - Article
C2 - 32452130
AN - SCOPUS:85087911468
SN - 1433-7851
VL - 59
SP - 14781
EP - 14787
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 35
ER -