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Proton-conducting layered structures based on transition metal oxo-clusters supported by Sb(iii) tartrate scaffolds
Wen Ma1, Bing Hu, Kaiqiang Jing
1State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China. xyhuang@fjirsm.ac.cn hubing@fjirsm.ac.cn.
Abstract:
Two transition metal-antimony oxo-cluster based compounds, H5{MCd(H2O)6[M(H2O)3Co3SbVSb(μ3-O)8(l-tta)6]}·7H2O (1) (M = Cd0.5 + Co0.5) and H3K5(H2O)11{Cd(H2O)4[Cd(H2O)Fe4Cd2Sb6(μ4-O)5(μ3-O)3(l-tta)6][Cd(H2O)2Fe4Cd2Sb6(μ4-O)4(μ3-O)4(l-tta)6][Cd(H2O)2Fe4Cd2Sb6(μ4-O)4(μ3-O)4(l-tta)6Cd(H2O)5]}·17H2O (2) (L-H4tta = l-tartaric acid) were hydrothermally synthesized and characterized. Compound 1 features a [MCo3SbVSb(μ3-O)8(l-tta)6(H2O)3]9- cluster, while compound 2 contains three types of clusters, namely, [Cd(H2O)Fe4Cd2Sb6(μ4-O)5(μ3-O)3(l-tta)6]4-, [Cd(H2O)2Fe4Cd2Sb6(μ4-O)4(μ3-O)4(l-tta)6]4- and [Cd(H2O)2Fe4Cd2Sb6(μ4-O)4(μ3-O)4(l-tta)6Cd(H2O)5]2-. All the clusters are of sandwich-type with {Sb3(μ3-O)(l-tta)} scaffolds on the top and bottom. The Cd (and M in 1) ions interconnect the clusters into layered structures in both compounds. To the best of our knowledge, this is the first report of transition metal-antimony oxo-clusters that simultaneously contain the first-row and second-raw transition metal ions, and compound 1 represents the first example of such type of clusters that contain Sb(v). The two compounds exhibit proton conductivity with the values of 2.43 × 10-3 and 2.95 × 10-3 S cm-1 at 85 °C under 98% relative humidity, respectively.
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