Two Series of Lanthanide Coordination Polymers with 2-Methylenesuccinate: Magnetic Refrigerant, Slow Magnetic Relaxation, and Luminescence Properties

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• 作者：Zhong-Yi Li ; Bin Zhai ; Su-Zhi Li ; Guang-Xiu Cao ; Fu-Qiang Zhang ; Xiang-Fei Zhang ; Fu-Li Zhang ; Chi Zhang
• 刊名：Crystal Growth & Design
• 出版年：2016
• 出版时间：August 3, 2016
• 年：2016
• 卷：16
• 期：8
• 页码：4574-4581
• 全文大小：615K
• 年卷期：0
• ISSN：1528-7505

文摘

Two series of lanthanide coordination polymers based on 2-methylenesuccinate acid (H₂MSA) ligand, {[Ln(MSA)(NO₃)(H₂O)₂]·2H₂O}_n (Ln = Gd (1); Tb (2); Dy (3)) and {[Ln₂(MSA)₃(H₂O)₄]·3H₂O}_n (Ln = Gd (4); Tb (5); Dy (6)), have been synthesized. Compounds 1–3 exhibit a one-dimensional (1D) zigzag chain structure, in which the neighboring Gd³⁺ ions are connected by two carboxylate groups from different MSA^2– ligands. Compounds 4–6 all consist of unique 1D lanthanide-carboxylate building units [Ln₄(CO₂)₆]_n constructed from the adjacent Ln³⁺ ions and carboxyl groups of the H₂MSA ligands, which can further generate two-dimensional layer structures via the link of MSA^2–. The magnetic study reveals that the weak ferromagnetic interactions between adjacent Gd³⁺ ions both exist in 1 and 4. Meanwhile, 1 and 4 display significant cryogenic magnetocaloric effects with maximum −ΔS_m values of 38.86 and 39.31 J kg^–1 K^–1 at 2 K and 7 T, respectively, and 3 was found to exhibit slow relaxation of the magnetization. Solid state photoluminescence properties reveal that the Tb- and Dy-containing complexes 2, 3, 5, and 6 are photoluminescent materials.