Citation: LIU Sui-Jun, CUI Yu, SONG Wei-Chao, WANG Qing-Lun, BU Xian-He. Carboxylate-Bridged Tetranuclear Lanthanide Clusters: Magnetocaloric Effect and Slow Magnetic Relaxation[J]. Chinese Journal of Inorganic Chemistry, ;2015, 31(9): 1894-1902. doi: 10.11862/CJIC.2015.240
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By using carboxylate and chelating ligands, a family of tetranuclear lanthanide clusters, namely [Ln4(mnba)12(tzp)2(H2O)2] (Ln=Gd (1), Tb (2) and Er (3), Hmnba=m-nitrobenzoic acid, tzp=2-(1H-1, 2, 4-triazol-3-yl)pyridine), has been obtained under hydrothermal conditions. The three complexes exhibit linear tetranuclear clusters bridged by carboxylates with syn, syn-μ2-η1:η1 mode. Magnetic investigation indicates weak ferromagnetic interaction between adjacent GdⅢ or ErⅢ ions of the Ln4 cluster in 1 and 3, while weak intra-molecular antiferromagnetic interaction between TbⅢ ions and/or depopulation of the TbⅢ excited Stark sub-levels in 2. Complex 1 exhibits a significant magnetocaloric effect with -ΔSmmax=20.6 J·kg-1·k-1 and ac susceptibility measurements reveal frequency- and temperature-dependent out-of-phase signal under 5 kOe dc field in 3, being typical slow magnetic relaxation behavior due to strong anisotropy of ErⅢ and ferromagnetic coupling.
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