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Two Octanuclear {Cu4Ln4} (Ln = Dy or Tb) Complexes with a Butterfly-Shaped Unit Exhibiting Zero-Field Single-Molecule
Xiaoxi Zhao1, Ge Li1, Jingjing Ma1
1Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province and State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Special Function Materials and Structure Design, Ministry of Education, College of Chemistry and Chemical Engineering , Lanzhou University , Lanzhou 730000 , China.
Abstract:
One-pot reaction of an asymmetrical acylhydrazone ligand H3L with Ln(ClO4)3 and CuCl2 in MeOH and MeCN solvents resulted in two novel octanuclear complexes, [Cu4Dy4L4Cl6(CH3OH)8(H2O)4]·Cl2(CH3OH)9(H2O)3 (1) and [Cu4Tb4L4Cl6(CH3OH)2(H2O)10]·Cl2(H2O) (2). Single-crystal X-ray diffraction studies revealed that these two complexes are isostructural and can be viewed as being built from two {Cu2Ln2L2} (Ln = Dy or Tb) butterfly-shaped units. Direct current magnetic susceptibilities and field-dependent magnetization measurements demonstrated the presence of strong ferromagnetic interaction between CuII and LnIII and magnetic anisotropy. Furthermore, alternating current (ac) magnetic measurements illustrated that these two complexes showed temperature- and frequency-dependent signals in the out-of-phase ac susceptibility under zero applied field, which are typical features of the slow relaxation of the magnetization for 1 and 2. The effective energy barrier (Ueff) for 1 was 54 K, which is one of the highest Ueff values yet reported for CuII/LnIII single-molecule magnets.
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