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

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

doi:10.1021/ic302364d.s001

ic302364d_si_001.pdf (1.06 MB)

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 Kojima

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.