Inorganic Chemistry, Vol.55, No.15, 7637-7646, 2016
Electrochemical Li-Ion Intercalation in Octacyanotungstate-Bridged Coordination Polymer with Evidence of Three Magnetic Regimes
Discovery of novel compounds capable of electrochemical ion intercalation is a primary step toward development of advanced electrochemical devices such as batteries. Although cyano-bridged coordination polymers including Prussian blue analogues have been intensively investigated as ion intercalation materials, the solid-state electrochemistry of the octacyanotungstate-bridged coordination polymer has not been investigated. Here, we demonstrate that an octacyanotungstate-bridged coordination polymer Tb(H2O)(5)[W(CN)(8)] operates as a Li+-ion intercalation electrode material. The detailed magnetic measurements reveal that the tunable amount of intercalated Li+ ion in the solid-state redox reaction between paramagnetic [W-V(CN)(8)](3-) and diamagnetic [W-IV(CN)(8)](4-) in the framework enables the electrochemical control of different magnetic regimes. While the initial ferromagnetic long-range ordering is irreversibly lost upon lithium insertion, electrochemical switching between paramagnetic and short-range ordering regimes can be achieved.