High-Nuclearity 3d–4f Clusters as Enhanced Magnetic Coolers and Molecular Magnets

Four 52-metal-ion 3d-4f cluster complexes featuring a common core of Ln(42)M(10) (Ln = Gd(3+), Dy(3+); M = Co(2+/3+), Ni(2+)) were obtained through self-assembly of the metal ions templated by mixed anions (ClO(4)(-) and CO(3)(2-)). Magnetic studies revealed that the Gd(42)Co(10) and Gd(42)Ni(10) clusters exhibit the largest magnetocaloric effect (MCE) among any known 3d-4f complexes. Replacement of Gd(3+) ions with anisotropic Dy(3+) ions caused significant changes in the magnetic behavior of the clusters; both Dy(42)Co(10) and Dy(42)Ni(10) displayed slow relaxation of the magnetization.