Transition Metal-Substituted Double Dawson-Type Polyoxotungstates and Their Supramolecular Structures

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Contents Vol 63(1)

doi:10.1071/CH09145

Transition Metal-Substituted Double Dawson-Type Polyoxotungstates and Their Supramolecular Structures

Shuang Yao ^A, Zhiming Zhang ^A, Yangguang Li ^A, Enbo Wang ^A ^B

^A Key Laboratory of Polyoxometalate Science of Ministry of Education, Department of Chemistry, Northeast Normal University, Renmin Street No. 5268, Changchun, Jilin, 130024, China.
^B Corresponding author. Email: wangeb889@nenu.edu.cn





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Australian Journal of Chemistry 63(1) 96–102 http://dx.doi.org/10.1071/CH09145
Submitted: 11 March 2009 Accepted: 10 July 2009 Published online: 8 January 2010

Abstract

Reactions of hexavacant polyoxotungstate [H₂P₂W₁₂O₄₈]^12– ({P₂W₁₂}) with various transition metal cations lead to the isolation of three double Dawson-type polyoxotungstates: (C₄H₁₀NO)₁₂Na₂[α ₁-MnP₂W₁₇O₆₁]₂·7H₂O (1), [(CH₃)₂NH₂]₃K₂Na₁₁[α ₁-CoP₂W₁₇O₆₁]₂·30H₂O (2), and Na₈K₂[Fe₂(H₂O)₈(Fe₂P₂W₁₆O₆₀)₂]·41H₂O (3). Compound 1 has a one-dimensional (1D) supramolecular architecture built from a Mn-substituted double Dawson-type polyoxoanion (DDTP) [α ₁-MnP₂W₁₇O₆₁]₂ ^14–, morpholine, and lattice water molecules. Compound 2 has a 1D supramolecular structure built from the first Co-containing DDTP [α ₁-CoP₂W₁₇O₆₁]₂ ^16– connected via H-bonding interactions. Compound 3 has a 3D supramolecular structure built from a Fe-substituted DDTP [Fe₂(H₂O)₈(Fe₂P₂W₁₆O₆₀)₂]^10– and lattice water molecules. Electrocatalytic studies indicate that these three compounds all display electrocatalytic activity toward the reduction of nitrite.