New Photomagnetic Ionic Salts Based on [MoIV(CN)8]4− and [WIV(CN)8]4− Anions

Three new ionic salts containing [M(CN)8]4− (M = MoIV and WIV) were prepared using large complex cations based on a non-conventional motif built with the tris(2-aminoethyl)amine (noted hereafter tren) ligand, [{M’(tren)}3(μ-tren)]6+ (M’ = CuII and ZnII). The crystal structures of the three compounds show that the atomic arrangement is formed by relatively isolated anionic and cationic entities. The three compounds were irradiated with a blue light at low temperature, and show a significant photomagnetic effect. The remarkable properties of these compounds are (i) the long-lived photomagnetic metastable states for the [Mo(CN)8]4−-based compounds well above 200 K and (ii) the rare efficient photomagnetic properties of the [W(CN)8]4−-based compound. These photomagnetic properties are compared with the singlet-triplet conversion recently reported for the K4[Mo(CN)8]·2H2O compound.