Reversible Solid State Redox of an Octacyanometallate-Bridged Coordination Polymer by Electrochemical Ion Insertion/Extraction

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• 作者：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
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：April 1, 2013
• 年：2013
• 卷：52
• 期：7
• 页码：3772-3779
• 全文大小：493K
• 年卷期：v.52,no.7(April 1, 2013)
• ISSN：1520-510X

文摘

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]路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.