Systematic Investigation of Reaction‐Time Dependence of Three Series of Copper–Lanthanide/Lanthanide Coordination Polymers: Syntheses,Structures, Photoluminescence,and Magnetism |
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Authors: | Dr. Ju‐Wen Zhang Xiao‐Min Kan Bin‐Qiu Liu Guo‐Cheng Liu Dr. Ai‐Xiang Tian Prof. Xiu‐Li Wang |
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Affiliation: | Department of Chemistry, Bohai University, Jinzhou 121000 (P.R. China) |
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Abstract: | Three series of copper–lanthanide/lanthanide coordination polymers (CPs) LnIIICuIICuI(bct)3(H2O)2 [Ln=La ( 1 ), Ce ( 2 ), Pr ( 3 ), Nd ( 4 ), Sm ( 5 ), Eu ( 6 ), Gd ( 7 ), Tb ( 8 ), Dy ( 9 ), Er ( 10 ), Yb ( 11 ), and Lu ( 12 ), H2bct=2,5‐bis(carboxymethylmercapto)‐1,3,4‐thiadiazole acid], LnIIICuI(bct)2 [Ln=Ce ( 2 a ), Pr ( 3 a ), Nd ( 4 a ), Sm ( 5 a ), Eu ( 6 a ), Gd ( 7 a ), Tb ( 8 a ), Dy ( 9 a ), Er ( 10 a ), Yb ( 11 a ), and Lu ( 12 a )], and LnIII2(bct)3(H2O)5 [Ln=La ( 1 b ), Ce ( 2 b ), Pr ( 3 b ), Nd ( 4 b ), Sm ( 5 b ), Eu ( 6 b ), Gd ( 7 b ), Tb ( 8 b ), and Dy ( 9 b )] have been successfully constructed under hydrothermal conditions by modulating the reaction time. Structural characterization has revealed that CPs 1 – 12 possess a unique one‐dimensional (1D) strip‐shaped structure containing two types of double‐helical chains and a double‐helical channel. CPs 2 a – 12 a show a three‐dimensional (3D) framework formed by CuI linking two types of homochiral layers with double‐helical channels. CPs 1 b – 9 b exhibit a 3D framework with single‐helical channels. CPs 6 b and 8 b display visible red and green luminescence of the EuIII and TbIII ions, respectively, sensitized by the bct ligand, and microsecond‐level lifetimes. CP 8 b shows a rare magnetic transition between short‐range ferromagnetic ordering at 110 K and long‐range ferromagnetic ordering below 10 K. CPs 9 a and 9 b display field‐induced single‐chain magnet (SCM) and/or single‐molecule magnet (SMM) behaviors, with Ueff values of 51.7 and 36.5 K, respectively. |
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Keywords: | copper lanthanides magnetism photoluminescence reaction times |
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