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Three new MOFs with unusual CuII 6 cluster, linear CuII chain and triangular CuII 3 core motifs tuned by sulfonate group: Synthesis, structures and magnetic properties

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Abstract

Three new MOFs with the same components but different structures and magnetic behavior, {[Cu6(atr)6(H2O)2(µ3-OH)2(SO4)5]·5.25H2O} n (1), {[Cu2(atr)2(µ-OH)2(SO4)]·3H2O} n (2), and {[Cu7(atr)6(H2O)6(µ3-OH)2(SO4)6]·2H2O} n (3) (atr = 4-amino-1,2,4-triazole), were respectively synthesized by diffusion reactions in the presence of different structure-directing agents. Complex 1 is a slightly spin-frustrated antiferromagnetic layer with sulfonate aggregated CuII 6 clusters periodically extended by ditopic sulfonate linkers. 2 is a grid-based coplanar sheet with hydroxyl group bridged -CuOCu- linear-chain interlinked by pairs of µ3-atr ligands, exhibiting strong antiferromagnetic interactions to lead to an S = 0 spin ground state at low temperature. In contrast, air-instable 3 has a ladder-like broad-ribbon structure constructed from triangular CuII 3 cores and centrosymmetric CuII 1 octahedra. Obviously, the variable CuII-ligand connectivity and the involving magnetic properties are significantly dominated by the cooperative and variable binding modes of the mixed sulfonate-atr ligands and bi-/tridentate bridging hydroxyl heterobridges.

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Authors and Affiliations

  1. Tianjin Key Laboratory of Structure and Performance for Functional Molecules; Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry, Ministry of Education; College of Chemistry, Tianjin Normal University, Tianjin, 300387, China

    EnCui Yang, XiuGuang Wang, CuiHua Zhang, Na Yang, ZhongYi Liu & XiaoJun Zhao

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  1. EnCui Yang
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  2. XiuGuang Wang
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  3. CuiHua Zhang
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  4. Na Yang
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  6. XiaoJun Zhao
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Correspondence to EnCui Yang or XiaoJun Zhao.

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Yang, E., Wang, X., Zhang, C. et al. Three new MOFs with unusual CuII 6 cluster, linear CuII chain and triangular CuII 3 core motifs tuned by sulfonate group: Synthesis, structures and magnetic properties. Sci. China Chem. 56, 465–474 (2013). https://doi.org/10.1007/s11426-012-4782-8

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