Reversible solid state redox of an octacyanometallate-bridged coordination polymer by electrochemical ion insertion/extraction

Masashi Okubo; Koichi Kagesawa; Yoshifumi Mizuno; Daisuke Asakura; Eiji Hosono; Tetsuichi Kudo; Haoshen Zhou; Kotaro Fujii; Hidehiro Uekusa; Shin Ichi Nishimura; Atsuo Yamada; Atsushi Okazawa; Norimichi Kojima

doi:10.1021/ic302364d

Reversible solid state redox of an octacyanometallate-bridged coordination polymer by electrochemical ion insertion/extraction

Masashi Okubo^*, Koichi Kagesawa, Yoshifumi Mizuno, Daisuke Asakura, Eiji Hosono, Tetsuichi Kudo, Haoshen Zhou, Kotaro Fujii, Hidehiro Uekusa, Shin Ichi Nishimura, Atsuo Yamada, Atsushi Okazawa, Norimichi Kojima

^*Corresponding author for this work

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

26 Citations (Scopus)

Abstract

Coordination polymers have significant potential for new functionality paradigms due to the intrinsic tunability of both their electronic and structural properties. In particular, octacyanometallate-bridged coordination polymers have the extended structural and magnetic diversity to achieve novel functionalities. We demonstrate that [Mn(H₂O)][Mn(HCOO) _2/3(H₂O)_2/3]_3/4[Mo(CN) ₈]·H₂O can exhibit electrochemical alkali-ion insertion/extraction with high durability. The high durability is explained by the small lattice change of less than 1% during the reaction, as evidenced by ex situ X-ray diffraction analysis. The ex situ X-ray absorption spectroscopy revealed reversible redox of the octacyanometallate. Furthermore, the solid state redox of the paramagnetic [Mo^V(CN)₈] ^3-/diamagnetic[Mo^IV(CN)₈]^4- couple realizes magnetic switching.

Original language	English
Pages (from-to)	3772-3779
Number of pages	8
Journal	Inorganic Chemistry
Volume	52
Issue number	7
DOIs	https://doi.org/10.1021/ic302364d
Publication status	Published - 2013 Apr 1
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Reversible solid state redox of an octacyanometallate-bridged coordination polymer by electrochemical ion insertion/extraction",

abstract = "Coordination polymers have significant potential for new functionality paradigms due to the intrinsic tunability of both their electronic and structural properties. In particular, octacyanometallate-bridged coordination polymers have the extended structural and magnetic diversity to achieve novel functionalities. We demonstrate that [Mn(H2O)][Mn(HCOO) 2/3(H2O)2/3]3/4[Mo(CN) 8]·H2O can exhibit electrochemical alkali-ion insertion/extraction with high durability. The high durability is explained by the small lattice change of less than 1% during the reaction, as evidenced by ex situ X-ray diffraction analysis. The ex situ X-ray absorption spectroscopy revealed reversible redox of the octacyanometallate. Furthermore, the solid state redox of the paramagnetic [MoV(CN)8] 3-/diamagnetic[MoIV(CN)8]4- couple realizes magnetic switching.",

author = "Masashi Okubo and Koichi Kagesawa and Yoshifumi Mizuno and Daisuke Asakura and Eiji Hosono and Tetsuichi Kudo and Haoshen Zhou and Kotaro Fujii and Hidehiro Uekusa and Nishimura, {Shin Ichi} and Atsuo Yamada and Atsushi Okazawa and Norimichi Kojima",

year = "2013",

month = apr,

day = "1",

doi = "10.1021/ic302364d",

language = "English",

volume = "52",

pages = "3772--3779",

journal = "Inorganic Chemistry",

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T1 - Reversible solid state redox of an octacyanometallate-bridged coordination polymer by electrochemical ion insertion/extraction

AU - Okubo, Masashi

AU - Kagesawa, Koichi

AU - Mizuno, Yoshifumi

AU - Asakura, Daisuke

AU - Hosono, Eiji

AU - Kudo, Tetsuichi

AU - Zhou, Haoshen

AU - Fujii, Kotaro

AU - Uekusa, Hidehiro

AU - Nishimura, Shin Ichi

AU - Yamada, Atsuo

AU - Okazawa, Atsushi

AU - Kojima, Norimichi

PY - 2013/4/1

Y1 - 2013/4/1

N2 - Coordination polymers have significant potential for new functionality paradigms due to the intrinsic tunability of both their electronic and structural properties. In particular, octacyanometallate-bridged coordination polymers have the extended structural and magnetic diversity to achieve novel functionalities. We demonstrate that [Mn(H2O)][Mn(HCOO) 2/3(H2O)2/3]3/4[Mo(CN) 8]·H2O can exhibit electrochemical alkali-ion insertion/extraction with high durability. The high durability is explained by the small lattice change of less than 1% during the reaction, as evidenced by ex situ X-ray diffraction analysis. The ex situ X-ray absorption spectroscopy revealed reversible redox of the octacyanometallate. Furthermore, the solid state redox of the paramagnetic [MoV(CN)8] 3-/diamagnetic[MoIV(CN)8]4- couple realizes magnetic switching.

AB - Coordination polymers have significant potential for new functionality paradigms due to the intrinsic tunability of both their electronic and structural properties. In particular, octacyanometallate-bridged coordination polymers have the extended structural and magnetic diversity to achieve novel functionalities. We demonstrate that [Mn(H2O)][Mn(HCOO) 2/3(H2O)2/3]3/4[Mo(CN) 8]·H2O can exhibit electrochemical alkali-ion insertion/extraction with high durability. The high durability is explained by the small lattice change of less than 1% during the reaction, as evidenced by ex situ X-ray diffraction analysis. The ex situ X-ray absorption spectroscopy revealed reversible redox of the octacyanometallate. Furthermore, the solid state redox of the paramagnetic [MoV(CN)8] 3-/diamagnetic[MoIV(CN)8]4- couple realizes magnetic switching.

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JO - Inorganic Chemistry

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Reversible solid state redox of an octacyanometallate-bridged coordination polymer by electrochemical ion insertion/extraction

Abstract

ASJC Scopus subject areas

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