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Two Hexa-Ni-Substituted AsW9O34 Clusters Functionalized by Organic Ligands |
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| Authors: | Bin Cai Jun-Wei Zhao Bai-Feng Yang Huan He Guo-Yu Yang |
| Institution: | 1. MOE Key Laboratory of Cluster Science, School of Chemistry, Beijing Institute of Technology, Beijing, 100081, China 2. Henan Key Laboratory of Polyoxometalate Chemistry, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, 475004, Henan, China 3. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, Fujian, China |
| Abstract: | Hydrothermal reactions of trilacunary precursor A-α-AsW9O34 9? polyoxoanions and nickel ions in the presence of ethylenediamine (en = ethylenediamine) led to two new hexa-Ni-substituted Keggin-type tungstoarsenates Ni6(μ 3-OH)3(en)3(H2O)6(B-α-AsW9O34)]·6H2O (1) and Ni6(μ 3-OH)3(en)3(H2O)6(B-α-AsW9O34)]·10H2O (2), which have been characterized by elemental analyses, IR spectra, powder X-ray diffraction, thermogravimetric analyses and single-crystal X-ray diffraction. Crystal data for 1: hexagonal, R3c, a = b = 20.4379(5) Å, c = 21.5062(6) Å, β = 120º, V = 7779.8 (3) Å3 and Z = 6; for 2: momoclinic, P21/c, a = 13.4200(3) Å, b = 19.1428(5) Å, c = 22.8845(9) Å, β = 112.403(3)º, V = 5435.2(3) Å3 and Z = 4. Structural analyses reveal that the Ni6(μ 3-OH)3(B-α-AsW9O34)] clusters in 1 and 2 are covalently functionalized by neutral en ligands, in which two similar {Ni6(μ 3-OH)3(en)3(H2O)6}9+ cores have been observed by our lab. Notably, 1 and 2 represent the highest number of substituted transition metal ions in all known lacunary Keggin-type polyoxotungstoarsenate monomers. |
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