Novel Rare Earth Germanotungstates and Organic Hybrid Derivatives: Synthesis and Structures of M/[α-GeW11O39] (M = Nd, Sm, Y, Yb) and Sm/[α-GeW11O39](DMSO)

Five novel polyoxometalate compounds built on the lacunary Keggin-type polyanion [GeW 11 O 39 ] 8- and trivalent rare earth ions (M = Nd, Sm, Y, Yb), [(CH 3 ) 4 N] 2 H 1.50 [Nd 1.50 (GeW 11 O 39 )(H 2 O) 6 ]·3H 2 O ( 1 ), [(CH 3 ) 4 N] 2 H 2.25 [Sm 1.25 (GeW 11 O 39 ) (H 2 O) 4 ]·3.75H 2 O ( 2 ), [(CH 3 ) 4 N] 2.50 H 2.50 [Y(GeW 11 O 39 )(H 2 O) 2 ]·4H 2 O ( 3 ), [(CH 3 ) 4 N] 2.50 H 2.50 Yb(GeW 11 O 39 )(H 2 O) 2 ]·3.75H 2 O ( 4 ), and [Sm(H 2 O) 7 ] 0.5 H 0.5 [Sm 2 (GeW 11 O 39 )(DMSO) 3 (H 2 O) 6 ]·3.5H 2 O ( 5 ) (DMSO = dimethyl sulfoxide) have been synthesized and characterized by elemental analysis, IR and UV spectroscopy, and single-crystal X-ray diffraction. The solid-state structures of compounds 1 and 2 consist of one-dimensional zigzag chains built of [α-GeW 11 O 39 ] 8- anions connected by Nd 3+ /Sm 3+ cations, while the linkage of the building blocks by Y 3+ /Yb 3+ centers in 3 and 4 leads to the formation of linear wires. Compound 5 displays a double-parallel chainlike structure constructed by two linear wires linked by samarium coordination cations.