The Versatility of Ethylene Glycol to Tune the Dimensionality and Magnetic Properties in Dy(III)-Anilato-Based Single-Ion Magnets

[Image: see text] We exploit the high versatility of the solvent ethylene glycol (eg = CH(2)OH-CH(2)OH) acting as a ligand with three different coordination modes: terminal (κO), chelate (κ(2)O,O′), and bridge (1κO,2κO′) to prepare a novel family of six different coordination polymers with Dy(III) and three different anilato ligands (3,6-disubstituted-2,5-dihydroxy-1,4-benzoquinone dianion = C(6)O(4)X(2)(2–), with X = H, Cl, and Br). With the X = H derivative (dhbq(2–)), we have prepared [Dy(2)(dhbq)(3)(eg)(2)(μ-eg)]·4eg·2H(2)O (1), a 3D diamond-like network with a chelate and bridging eg molecules. With the X = Cl derivative (chloranilato), we have prepared [Dy(2)(C(6)O(4)Cl(2))(3)(eg)(4)]·2eg·H(2)O (2) and [Dy(2)(C(6)O(4)Cl(2))(3)(μ-eg)(H(2)O)(4)]·2eg·7H(2)O (3). Compound 2 has a 2D (6,3)-gon brick-wall lattice and contains a chelate and a terminal eg molecule. Compound 3 has a 3D diamond-like topology as 1, although now the chelate eg has been replaced by two water molecules. Finally, with the X = Br derivative (bromanilato), we have obtained [Dy(2)(C(6)O(4)Br(2))(3)(eg)(2)(CH(3)OH)(2)]·2eg·4CH(3)OH (4), [Dy(2)(C(6)O(4)Br(2))(3)(eg)(4)]·4eg (5), and [Dy(2)(C(6)O(4)Br(2))(3)(eg)(3)(H(2)O)]·2eg·H(2)O (6). Compound 4 has a 2D (6,3)-gon herringbone topology and contains a chelate eg and a MeOH molecule. Compounds 5 and 6 have a 2D (6,3)-gon brick-wall topology with a chelate and a terminal eg molecules (in 5 and in one of the two independent Dy centers of 6). The other Dy center in 6 has a chelate eg and a water molecule. All the compounds show slow relaxation of the magnetization at low temperatures (in compounds 1, 2, and 5 with no applied DC field). The magnetization of compounds 1–6 relaxes through Orbach and direct mechanisms when a DC field is applied and through an Orbach and/or quantum tunneling mechanism when no DC field is applied.