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] (<b>1</b>) and [Dy₄(H₂L′)₄M_<i>x</i>(SCN)₈] (M_<i>x</i> = Co₃ (<b>2</b>); M_<i>x</i> = Cu₅ (<b>3</b>)), 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 <b>1</b> were filled with the large inorganic ions [Co₃(SCN)₄]²⁺ and [Cu₅(SCN)₄]⁶⁺ in complexes <b>2</b> and <b>3</b>, respectively, forming the first [3 × 2] and [3 × 3] 3d–4f gridlike structures. Additionally, magnetic studies show that complex <b>1</b> exhibits field-induced SMM behavior and double magnetic relaxation, while complexes <b>2</b> and <b>3</b> display typical SMM behavior at zero applied field