A Polyoxometalate Containing Circular {P 5 W 30 } Units and Cubic {Cu 4 } Clusters

A polyoxometalate (POM) based on the assembly of [P 5 W 30 O 110 ] 15– ({P 5 W 30 }) units and copper ions, {(H 5 P 5 W 30 O 110 ) 2 [(en) 4 Cu 4 (μ 3 ‐OH) 3 (μ‐H 2 O)] 2 }[Cu(en) 2 ] 4 [Cu(H 2 O) 3 ] · 12H 2 O (en = ethylenediamine) ( 1 ), has been made under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction (XRD), elemental analysis, IR spectroscopy, thermogravimetric analysis, and power XRD; saturated {P 5 W 30 } was used as the precursor to make the new POM. POM 1 is the first 3D {P 5 W 30 }‐based POM linked by late transition metal copper complex ions, and it also features the rarely seen linkages of the saturated {P 5 W 30 } units and [Cu 4 (μ 3 ‐OH) 3 (μ‐H 2 O)] ({Cu 4 }) clusters. In the structure of 1 , the {P 5 W 30 } units and {Cu 4 } clusters are alternately linked to form dimeric units and are further connected by two kinds of [Cu(en) 2 ] 2+ complex bridges, which results in the 3D framework.