Concise Chemistry Modulation of the SMM Behavior within a Family of Mononuclear Dy(III) Complexes

By means of the facile chemistry, structural assembly, and transformation of four mononuclear Dy(III) complexes, Dy(bpad)₃·CH₃OH·H₂O (1), Dy(bpad)₂(H₂O)₂·NO₃ (2), [Dy(bpad)₂(tmhd)] (3), and [Dy(bpad)₂(btfa)] (4) (Hbpad = N³-benzoylpyridine-2-carboxamidrazone, tmhd = 2,2,6,6-tetramethylheptane-3,5-dione, btfa = 3-benzoyl-1,1,1-trifluoroacetone), with distinct architectures and local symmetries were established. The disparity of the coordination geometries around the Dy(III) ion among these complexes impacts the strength of the crystal field and the local tensor of anisotropy ( D) of each Dy site and their relative orientations, therefore giving rise to diverse SIM behaviors with distinguishing relaxation energy barriers of 106.93 K for 1, 52.55 K for 2, 48.16 K for 3, and 51.41 K for 4. The differences of the magnetic property and the magnetic anisotropy for four complexes have been explained by ab initio calculations, which are corresponding to the experimental results.