Designing Ligands to Isolate ZnLn and Zn2Ln Complexes: Field-Induced Single-Ion Magnet Behavior of the ZnDy, Zn2Dy, and Zn2Er Analogues.

ABSTRACT

A new H3L Schiff base ligand with three defined compartments, namely, two internal NNO and one external O6, was designed to allocate metal ions of different size. This ligand allows isolating heterodinuclear [ZnLn(HL)(NO3)(OAc)(D)](NO3) (Ln = Tb, D = H2O, ZnTb; Ln = Dy, D = CH3OH, ZnDy; and Ln = Er, D = CH3OH, ZnEr) complexes, where one of the NNO pockets allocates a zinc(II) ion, while the other one is empty, or heterotrinuclear [Zn2Ln(L)(NO3)2(OAc)2(H2O)] (Ln = Dy, Zn2Dy and Ln = Er, Zn2Er) compounds, where each NNO compartment accommodates ZnII. All these compounds crystallize with different solvates, and their structures were unequivocally determined by single-crystal X-ray diffraction studies. Complexes ZnDy, Zn2Dy, and Zn2Er behave as single-molecule magnets in the presence of an external dc field of 1000 Oe, with Ueff values of 41.05, 47.69, and 20.81 K, respectively, while ZnTb and ZnEr do not.