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The syntheses of two new polynuclear TbIII compounds are reported. A tetranuclear complex [Tb4(H2L)2(H4L)2(OAc)8] (1), with H4L = 2-((2-hydroxy-benzylidene)-amino)-2-hydroxy-methyl-propane-1,3-diol, has a butterfly-type structure, while [Tb(OAc)3MeOH]∞ (2) is a linear chain. A novel binding mode for H2L2− is observed in 1, with two alkoxides each bridging three TbIII ions. The magnetic properties of 1 are determined by the superposition of the ligand field split 7F6 states of TbIII single-ions located on two crystallographically distinct sites. Weak antiferromagnetic exchange interactions possibly contribute to the lowering of the magnetic moment at the lowest temperatures.

The reaction of Ni(OAc)2, NiX2 (X = Cl, Br) or CoCl2 with the proligand 2-amino-2-methyl-1,3-propanediol (ampdH2) affords a new family of tetranuclear complexes. The syntheses of [Ni4(OAc)4(ampdH)4] (1) and [M4X4(ampdH)4] (M = Ni, X = Cl, 2; M = Ni, X = Br, 3; M = Co, X = Cl, 4) are reported, together with the single crystal X-ray structures of 1, 2 and 4 and the magnetochemical characterization of 1, 3 and 4. Each member of this family of complexes displays a low symmetry structure that incorporates a {M4O4} core unit based on a distorted cubane. Magnetic measurements reveal ferromagnetic exchange interactions for 1, 3 and 4. These give rise to S = 4 ground state spins for the tetranuclear Ni complexes and an anisotropic effective S′ = 2 ground state for the Co complex.

We report on the magnetic properties of the enneanuclear mixed-valent single-molecule magnet [Mn9O7(OAc)11(thme)(py)3(H2O)2] (1). Using inelastic neutron scattering (INS) spectroscopy, we have confirmed the S = 17/2 cluster ground state of 1. Furthermore, we have determined accurately the anisotropy parameters of the zero field split ground state. The cluster 1 exhibits a strong negative axial anisotropy D [ S ˆ z 2 - S ( S + 1 ) / 3 ] where D = −0.249(5) cm−1. It is necessary to include an axial higher order term ( B 4 0 ) in the effective spin Hamiltonian to account for the experimental data.