Light-induced synthesis of an octacyanometalate-based three-dimensional bimetallic complex [Mn3Mo2]∞

Under light irradiation, (Bu3NH)3[MoV(CN)8]·2H2O reacting with MnClO4·6H2O and NH4SCN leads to the formation of a new three-dimensional cyano-bridged bimetallic complex {(NH4)2[MnII(CH3OH)4][MnII(DMF)]2[MoIV(CN)8]2}∞ (1). X-ray crystallographic analysis reveals that complex 1 crystallizes in a monoclinic space group and contains two different coordination configurations around MnII ions in an asymmetric unit. Specifically, one is six-coordinated while the other is five-coordinated. The magnetic investigation shows that the paramagnetic behavior is only ascribed to MnII ions because MoV has been reduced into diamagnetic MoIV.