Diverse Lanthanide Coordination Polymers with 3,3'-Dimethylcyclopropane-1,2-dicarboxylate Ligand: Synthesis, Crystal...

In an attempt to investigate the influence of many variables on the synthesis of lanthanide coordination polymers (Ln-CPs) assembled from the ligand 3,3-dimethylcyclopropane-1,2-dicarboxylic acid, three different Ln-CPs with formulae [La₉(μ₄-dcd)₁₂(μ₃-O)₂(H)] (1), [Gd₄(μ₄-dcd)₆(H₂O)] (2), and [Gd₂(μ₃-OH)₂(μ₃-dcd)(μ₂-ac)₂(H₂O)] (3) (dcd = 3,3-dimethylcyclopropane-1,2-dicarboxylate, ac = acetate) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, thermal analysis, powder X-ray diffraction, and single X-ray diffraction techniques. 1 represents the first report of the three-dimensional (3D) Ln-CPs based on nonanuclear lanthanide clusters, although it shows extremely low gas uptakes. 2 exhibits one of the previously reported 3D lanthanide wheel cluster-like frameworks. 3 characterizes a novel one-dimensional ladder-like chain [Gd₄(OH)₄] decorated with mixed ligand ribbons. Variable-temperature magnetic susceptibility measurement reveals that the shortest Gd···Gd distance in 3 induces the antiferromagnetic interactions between adjacent Gd³⁺ cations within the hydroxyl-bridged binuclear unit. Remarkably, magnetic investigation for 2 indicates a unique metamagnetic transition from the antiferromagnet to ferromagnet. Furthermore, magnetic studies for 2 also exhibit the presence of significant magnetocaloric effect with a large magnetic entropy change.