Electron Transfer, Linkage Isomerization, Bulk Magnetic Order, and Spin-Glass Behavior in the Iron Hexacyanomanganate Prussian Blue Analogue

Unexpected electron transfer and linkage isomerization led to the formation of FeII0.23FeIII0.72MnIII0.02MnIV0.03[MnIV(CN)6]0.23[MnIII(CN)6]0.72[FeIII(CN)6]0.02[FeII-(CN)6]0.03 from the reaction of [FeII(NCMe)6]2+and [MnIV(CN)6]2−. Hydration leads to further electron transfer and linkage isomerization to form {FeII0.15FeIII0.80MnIII0.01MnIV0.04[MnIV(CN)6]0.15[MnIII[CN)6]0.80FeIII(CN)6]0.01FeII(CN)6]0.04}⋅x H2O, which upon heating forms {FeIII0.94MnIV0.06[MnIII(CN)6]0.94[FeII(CN)6]0.06}⋅x H2O.