{W48} ring opening: Fe16-containing, Ln4-stabilized 49-tungsto-8-phosphateopen wheel [Fe16O2(OH)23(H2O)9(P8W49O189)Ln4(H2O)20]11-.

Wheely: For the first time and very unexpectedly, a rupture of the very stable {P(8)W(48)} wheel was observed in aqueous solution at pH 4 and 80 °C in the presence of Fe(III), Eu(III)/Gd(III), and H(2)O(2). This inorganic ring opening is unprecedented in polyoxometalate chemistry.

22-Isopolytungstate fragment [H2W22O74]14- coordinated to lanthanide ions.

The novel polyanions [Ln(2)(H(2)O)(10)W(22)O(71)(OH)(2)](8-) (Ln = La (1), Ce (2), Tb (3), Dy (4), Ho (5), Er (6), Tm (7), Yb (8), Lu (9), Y (10)) have been synthesized by reaction of WO(4)(2-) and lanthanide ions in acidic aqueous medium. The low symmetry (C(i)) polyanion family [Ln(2)(H(2)O)(10)W(22)O(71)(OH)(2)](8-) consists of the isopolyanion [H(2)W(22)O(74)](14-) and two {Ln(H(2)O)(5)}(3+) supporting units. The [H(2)W(22)O(74)](14-) cluster, which consists of two undecatungstate {W(11)} fragments, acts as a tridentate ligand to two Ln(3+) ions. Polyanions 1-10 are isostructural, and the coordination number of the lanthanide ions correlates with their sizes. All compounds have been fully characterized in the solid state by Fourier transform infrared spectroscopy, single-crystal X-ray diffraction, thermogravimetric analysis, and elemental analysis. Single-crystal X-ray diffraction analyses show that 1-10 crystallize as sodium salts in the triclinic space group P1.

Copper-, cobalt-, and manganese-containing 17-tungsto-2-germanates.

The sandwich-type tungstogermanates [Cu(3)(H(2)O)(B-beta-GeW(9)O(33)(OH))(B-beta-GeW(8)O(30)(OH))](12-) (1), [Co(H(2)O)(2){Co(3)(B-beta-GeW(9)O(33)(OH))(B-beta-GeW(8)O(30)(OH))}(2)](22-) (2), and [Mn(H(2)O)(2){Mn(3)(H(2)O)(B-beta-GeW(9)O(33)(OH))(B-beta-GeW(8)O(30)(OH))}(2)](22-) (3) were synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, thermogravimetric analysis, and infrared spectroscopy. Polyanion 1 is composed of two nonequivalent Keggin units, (B-beta-GeW(8)O(31)) and (B-beta-GeW(9)O(34)), linked to each other via three copper(II) ions in such a way that there is a plane of symmetry passing through both Ge atoms and the unique Cu atom, resulting in a sandwich-type structure with C(s) symmetry. On the other hand, the monomeric building blocks of 2 and 3 contain the same Keggin fragments as 1, but linked through three octahedrally coordinated Co(2+) or Mn(2+) ions. The major difference between complex 1 and complexes 2 and 3 is that the latter all lack a plane of symmetry due to a different orientation of the rotated triad. Magnetic measurements indicated antiferromagnetic exchange interactions between the three Cu(2+) ions in 1 and between the three Mn(2+) ions in 3. On the other hand, polyanion 2 possesses ferromagnetic interaction of the Co(2+) ions. The best least-squares fit values for 2 are J(z) = 7.9 cm(-1), J(z) = 3.1 cm(-1), J(y) = 2.4 cm(-1), g(z) = 6.77 cm(-1), and g(xy) = 4.15 (R = 2.6 x 10(-2)).