title: New Family of Octagonal-Prismatic Lanthanide Coordination Cages Assembled from Unique Ln17 Clusters and Simple Cliplike Dicarboxylate Ligands.
abstract: 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.
authors.affiliation: Key Laboratory of Chemical Sensing and Analysis in Universities of Shandong, School of Chemistry and Chemical Engineering, and ‡Shandong Provincial Key Laboratory of Fluorine Chemistry and Chemical Materials, School of Chemistry and Chemical Engineering, University of Jinan , Jinan 250022, P. R. China.
authors.forename: Yuan-Yuan
authors.initials: YY
authors.lastname: Zhou
authors.affiliation: Key Laboratory of Chemical Sensing and Analysis in Universities of Shandong, School of Chemistry and Chemical Engineering, and ‡Shandong Provincial Key Laboratory of Fluorine Chemistry and Chemical Materials, School of Chemistry and Chemical Engineering, University of Jinan , Jinan 250022, P. R. China.
authors.forename: Bing
authors.initials: B
authors.lastname: Geng
authors.affiliation: Key Laboratory of Chemical Sensing and Analysis in Universities of Shandong, School of Chemistry and Chemical Engineering, and ‡Shandong Provincial Key Laboratory of Fluorine Chemistry and Chemical Materials, School of Chemistry and Chemical Engineering, University of Jinan , Jinan 250022, P. R. China.
authors.forename: Zhen-Wei
authors.initials: ZW
authors.lastname: Zhang
authors.affiliation: Key Laboratory of Chemical Sensing and Analysis in Universities of Shandong, School of Chemistry and Chemical Engineering, and ‡Shandong Provincial Key Laboratory of Fluorine Chemistry and Chemical Materials, School of Chemistry and Chemical Engineering, University of Jinan , Jinan 250022, P. R. China.
authors.forename: Qun
authors.initials: Q
authors.lastname: Guan
authors.affiliation: Key Laboratory of Chemical Sensing and Analysis in Universities of Shandong, School of Chemistry and Chemical Engineering, and ‡Shandong Provincial Key Laboratory of Fluorine Chemistry and Chemical Materials, School of Chemistry and Chemical Engineering, University of Jinan , Jinan 250022, P. R. China.
authors.forename: Jun-Ling
authors.initials: JL
authors.lastname: Lu
authors.affiliation: Key Laboratory of Chemical Sensing and Analysis in Universities of Shandong, School of Chemistry and Chemical Engineering, and ‡Shandong Provincial Key Laboratory of Fluorine Chemistry and Chemical Materials, School of Chemistry and Chemical Engineering, University of Jinan , Jinan 250022, P. R. China.
authors.forename: Qi-Bing
authors.initials: QB
authors.lastname: Bo