Syntheses, Structures and Spectroscopic Characterization of Extended Waugh‐Type Polyoxometalates with Metal Ions as Linkers

Abstract Two extended Waugh‐type polyoxometalates compounds, (NH4)4Na2[MnMo9O32]·6H2O (1) and (NH4)2Na2[{Cu(H2O)4}(MnMo9O32)]·5H2O (2) have been synthesized and characterized. Both of the left‐handed and right‐handed [MnMo9O32]6− polyanions enantiomers can be observed in compounds 1 and 2. In compound 1, the homochiral [MnMo9O32]6− polyanions enantiomers are linked by sodium ions to form two kinds of alternately arranged 2D polymeric sheets, which are further stacked into a 3D framework. In compound 2, the homochiral [MnMo9O32]6− polyanions enantiomers are linked by [(H2O)2Cu(μ2‐H2O)2Na(H2O)2]3+ bimetal aggregates to form two kinds of alternately arranged zigzag chains, which are further weaved into a 2D polymeric sheet by sodium ions. In addition, the influence of the synthesis conditions has also been studied.