Metallosupramolecular Coordination Complexes: The Design of Heterometallic 3d–4f Gridlike Structures

A series of mixed metal 3d–4f gridlike structures, [Dy4(H2L′)4Zn4(SCN)4] (1) and [Dy4(H2L′)4Mx(SCN)8] (Mx = Co3 (2); Mx = Cu5 (3)), showing Chinese hieroglyph like [2 × 2], [3 × 2], and [3 × 3] matrixes, were assembled and magnetically characterized. Remarkably, the empty cage constructed by the oblique organic ligands and SCN– ions in complex 1 were filled with the large inorganic ions [Co3(SCN)4]2+ and [Cu5(SCN)4]6+ in complexes 2 and 3, respectively, forming the first [3 × 2] and [3 × 3] 3d–4f gridlike structures. Additionally, magnetic studies show that complex 1 exhibits field-induced SMM behavior and double magnetic relaxation, while complexes 2 and 3 display typical SMM behavior at zero applied field.