Two Types of Polyoxometalates Based on Circular P 8 W 48 Cluster Units and Different Inclusions of Tetralanthanide and Octamanganese Centers

Two types of new polyoxometalates (POMs) based on circular P 8 W 48 clusters with different tetralanthanide (Ln) clusters and octamanganese centers, [K(H 2 O) 2 ] 4 [K 4 (μ‐H 2 O) 4 (H 2 O) 4 ] 2 {[Ln 2 (μ‐OH) 4 (H 2 O) x ] 2 (H 24 P 8 W 48 O 184 )} · y H 2 O [Ln = Nd ( 1 ), Sm ( 2 ), Tb ( 3 )] and [K(H 2 O) 2 ] 4 [K 4 (μ‐H 2 O) 8 ] 2 [K(H 2 O)] 8 {[Mn 8 (H 2 O) 16 ](H 4 P 8 W 48 O 184 )} · 36H 2 O ( 4 ) have been synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction, elemental analysis, IR spectroscopy, thermogravimetry (TG), and powder XRD. Compounds 1 – 3 are the first series of Ln‐containing P 8 W 48 ‐based POMs that use P 2 W 12 O 48 14– as the precursor; previously known P 8 W 48 ‐based POMs used P 8 W 48 O 184 40– as the precursor. In 4 , eight manganese ions were incorporated. Owing to the different radii of the Ln and Mn ions, the four large Ln ions are divided into two {Ln 2 } clusters located on two sides of the cavity of the P 8 W 48 wheel in 1 – 3 , but the eight small manganese ions in 4 only bond to the inside of the P 8 W 48 wheel and do not form manganese clusters. The magnetic properties of 3 are discussed.