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Reversible Solid State Redox of an Octacyanometallate-Bridged Coordination Polymer by Electrochemical Ion Insertion/Extraction
journal contribution
posted on 2013-04-01, 00:00 authored by 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 KojimaCoordination
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.