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Synthesis, crystal structures, and magnetic properties of two three-dimensional octacyanotungstate(IV)-based bimetallic frameworks with 4,4′-bipyridine dioxide (4,4′-dpdo)

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Abstract

The reaction of [HN(n-C4H9)3]3[WV (CN)8]·4H2O, 4,4′-bipyridine dioxide(4,4′-dpdo), and MnCl2·4H2O or CuCl2·2H2O gives two new three-dimensional octacyanometalate-based bimetallic assemblies, {[Mn2 (4,4′-dpdo)(H2O)4] [WIV (CN)8]{·6H2O (1) and {[Cu2(4,4′-dpdo)(H2O)][W(CN)8]{·CH3OH·H2O (2). Compound 1 crystallizes in the orthorhombic system, space group P21212 with cell constants α=10.397(2) Å, b=11.321(2) Å, c=12.295(3) Å and Z=2, whereas 2 crystallizes in the monoclinic system, space group P21/c with cell constants a=13.038(3) Å, b=13.784(3) Å, c=13.225(3) Å, β=93.44(3)° and Z=4. In complex 1, each [WIV (CN)8]4− unit with a square antiprismatic geometry is connected to four Mn2 dimers through four bridging CN− ions forming wavelike alternating-W-Mn2-W-Mn2- layers, which are further linked through 4,4′-dpdo ligands coordinated to the Mn ions into a three-dimensional open framework. In complex 2, each [WIV (CN)8]4− ion still adopts a square antiprismatic geometry, whereas it bonds to seven copper ions through seven CN− ions leading to cage-like undulate layers further bridged by 4,4′-dpdo ligands into a three-dimensional network. Due to the bridging role of the long rigid 4,4′-dpdo ligand, there exist plenty of large cavities in the open frameworks of complexes 1 and 2 occupied by solvent clusters containing H2O or CH3OH molecules. To our knowledge, it is noted that 4,4′-dpdo displays a μ-4,4,4′,4′ mode, which was first experimentally observed, although predicted before. Magnetic studies show that complex 1 displays an antiferromagnetic coupling between MnII ions, while complex 2 exhibits a weak ferromagnetic interaction between CuII ions.

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Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences, and State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China

    Mei Yuan, Song Gao, Fei Zhao, Wen Zhang & ZheMing Wang

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  1. Mei Yuan
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Correspondence to Song Gao.

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Supported by the National Natural Science Foundation of China (Nos. 20221101, 20490210, and 20701039), and the National Basic Research Program of China (No. 2006CB601102)

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Yuan, M., Gao, S., Zhao, F. et al. Synthesis, crystal structures, and magnetic properties of two three-dimensional octacyanotungstate(IV)-based bimetallic frameworks with 4,4′-bipyridine dioxide (4,4′-dpdo). Sci. China Ser. B-Chem. 52, 266–275 (2009). https://doi.org/10.1007/s11426-009-0050-y

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