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

Two extended Waugh‐type polyoxometalates compounds, (NH 4 ) 4 Na 2 [MnMo 9 O 32 ]·6H 2 O ( 1 ) and (NH 4 ) 2 Na 2 [{Cu(H 2 O) 4 }(MnMo 9 O 32 )]·5H 2 O ( 2 ) have been synthesized and characterized. Both of the left‐handed and right‐handed [MnMo 9 O 32 ] 6− polyanions enantiomers can be observed in compounds 1 and 2 . In compound 1 , the homochiral [MnMo 9 O 32 ] 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 [MnMo 9 O 32 ] 6− polyanions enantiomers are linked by [(H 2 O) 2 Cu(μ 2 ‐H 2 O) 2 Na(H 2 O) 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.