An effective approach to layered structures of hybrid Prussian blue complexes:: Monolayered [Sm(DMF)2(H2O)3(μ-CN)3M(CN)3]n•nH2O and bilayered [Sm(DMF)(H2O)3(μ-CN)4M(CN)2]n•nH2O (M = Fe, Co)

Four cyano-bridged 4f-3d (lanthanide-transition metal) bimetallic assemblies, [Sm(DMF)(2)(H2O)(3)(mu-CN)(3)M(CN)(3)](n) center dot nH(2)O (M = Fe ( 1), Co (2)) with 2-D monolayered structures and [Sm(DMF)(H2O)(3)(mu-CN)(4)M(CN)(2)](n) center dot nH(2)O (M = Fe ( 3), Co ( 4)) with 2-D bilayered structures (DMF = N, N-dimethylformamide), were rationally prepared by a facile approach, a ball-milling method, and characterized by X-ray diffraction studies and magnetic measurements. The unprecedented 2-D bilayered 4f-3d hexacyanometalates ( 3 and 4) were obtained by controllably reducing the half amount of DMF in the reactive system in comparison with 1 and 2 through a ball-milling method.