Proton-conducting layered structures based on transition metal oxo-clusters supported by Sb(iii) tartrate scaffolds

Abstract

Two transition metal-antimony oxo-cluster based compounds, H₅{MCd(H₂O)₆[M(H₂O)₃Co₃Sb^VSb(μ₃-O)₈(l-tta)₆]}·7H₂O (1) (M = Cd_0.5 + Co_0.5) 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 [MCo₃Sb^VSb(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.