Metal-ion induced ferromagnetic polarization in a mixed-spin system

Abstract

Three new 3d–3d heterometallic complexes, [Cu^II₃M^II(hmb)₆(OH)]ClO₄·H₂O (M = Zn (1), Ni (2) and Co (3)) (Hhmb = 2-hydroxy-3-methoxy-benzaldehyde), have been synthesized. Structural analysis reveals that the three complexes are isostructural. Three Cu^II ions are in a perfect trigonal geometrical frustration and form a tetrahedral frustrated system with the introduced fourth ion Zn^II/Ni^II/Co^II. Magnetic studies indicate the antiferromagnetic coupling between metal ions in all 1, 2 and 3. Due to the geometrical frustration, spin-frustrated magnetism is also a typical feature of 1–3 and the magnetostructural correlation is far more complicated than their structures. The detailed magnetic investigation found that the ground state spin of 2 cannot be simply determined by the antiferromagnetically linear arrangement of spins, because the strong antiferromagnetic coupling between Cu^II and Ni^II ions quenches the spin frustration and ferromagnetically polarizes the spins of the [Cu^II₃] unit. Contrarily, the antiferromagnetic coupling between Cu^II and Co^II ions is not strong enough in 3, so there is no similar behaviour compared to 2.