New Family of Octagonal-Prismatic Lanthanide Coordination Cages Assembled from Unique Ln17 Clusters and Simple Cliplike Dicarboxylate Ligands

详细信息    查看全文

• 作者：Yuan-Yuan Zhou ; Bing Geng ; Zhen-Wei Zhang ; Qun Guan ; Jun-Ling Lu ; Qi-Bing Bo
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：March 7, 2016
• 年：2016
• 卷：55
• 期：5
• 页码：2037-2047
• 全文大小：872K
• ISSN：1520-510X

文摘

Novel high-nuclearity lanthanide clusters (Ln₁₇) are generated in situ in the coordination-driven self-assembly. A metal-cluster-directed symmetry strategy for building metal coordination cages is successfully applied to a lanthanide system for the first time. A new family of octagonal-prismatic lanthanide coordination cages UJN-Ln, formulated as [Ln(μ₃-OH)₈][Ln₁₆(μ₄-O)(μ₄-OH)(μ₃-OH)₈(H₂O)₈(μ₄-dcd)₈][(μ₃-dcd)₈]·22H₂O (Ln = Gd, Tb, Dy, Ho, and Er; dcd = 3,3-dimethylcyclopropane-1,2-dicarboxylate dianion), have been assembled from the unique Ln₁₇ clusters and simple cliplike ligand H₂dcd. Apart from featuring aesthetically charming structures, all of the compounds present predominantly antiferromagnetic coupling between the corresponding lanthanide ions. Additionally, the intense-green photoluminescence for UJN-Tb and magnetic relaxation behavior for UJN-Dy have been observed. Remarkably, UJN-Gd shows a large magnetocaloric effect (MCE) with an impressive entropy change value of 42.3 J kg^–1 K^–1 for ΔH = 7.0 T at 2.0 K due to the high-nuclearity cluster and the lightweight ligand. The studies highlight the structural diversity of multigonal-prismatic metal coordination cages and provide a new direction in the design of cagelike multifunctional materials by the introduction of lanthanide clusters and other suitable cliplike ligands.