New Strategies for the Generation of Large Heteropolymetalate Clusters: The β‐ B ‐SbW 9 Fragment as a Multifunctional Unit

Proceeding from the α‐ B ‐SbW 9 O 33 fragment 1 , various novel large heteropolyanions ([Na 2 Sb 8 W 36 O 132 (H 2 O) 4 ] 22– ( 2 ), [Sb 2 W 22 O 74 (OH) 2 ] 12− ( 3 ) and [Sb 2 W 20 M 2 O 70 (H 2 O) 6 ] (14−2 n )− ( 4 ); M n + = Fe 3+ , Co 2+ , Mn 2+ , Ni 2+ ) have been obtained in crystalline form by systematic synthesis. Their unexpected structures have been studied by X‐ray diffraction: 2, 3 and 4 contain β‐SbW 9 units connected to each other by Sb 3+ ions, WO 2 /WO 2 OH groups, and WO 2 /M n + (H 2 O) 3 groups, respectively. Structural details and especially the systematic synthesis strategy for the formation of these interesting polytungstates are discussed in order to explain the unusual behaviour of 1 in aqueous solution under different reaction conditions.