Mixed valency and magnetism in cyanometallates and Prussian blue analogues

Prussian blue (PB) is a well-known archetype of mixed valency systems. In magnetic PB analogues {CxAy[B(CN)6]z}.nH2O (C alkali cation, A and B transition metal ions) and other metallic cyanometallates {Cx(AL)y[B(CN)8]z}.nH2O (L ligand), the presence of two valency states in the solid (either A-B, or A-A' or B-B') is crucial to get original magnetic properties: tunable high Curie temperature magnets; photomagnetic magnets; or photomagnetic high-spin molecules. We focus on a few mixed valency pairs: V(II)/V(III)/V(IV); Cr(II)/Cr(III); Fe(II)-Fe(III); Co(II)-Co(III); Cu(I)-Cu(II); and Mo(IV)/Mo(V), and discuss: (i) the control of the degree of mixed valency during the synthesis, (ii) the importance of mixed valency on the local and long-range structure and on the local and macroscopic magnetization, and (iii) the crucial role of the cyanide ligand to get these original systems and properties.