The reaction of Na2WO4 and SeO2 under moderately acidic conditions yielded a novel 39-tungsto-6-selenite, [(Se2W12O46(WO(H2O))3](24-) (1), isolated as Na24[H6Se6W39O144]·74H2O. The macrocyclic polyanion consists of three {Se2W12} fragments connected via three trans-{WO(H2O)}(4+) groups. The same {Se2W12} building block is present in the structure of [(Se2W12O46)2{Mn2Cl(H2O)2}{Mn(H2O)2}2(SeO)2](13-) (2), which was obtained from the same reagents in the presence of MnCl2. The compounds were characterized by single-crystal X-ray diffraction, (77)Se NMR, Fourier transform infrared, and Raman spectroscopy.

The gallium(III)-containing heteropolytungstates [Ga4(H2O)10(β-XW9O33)2](6-) (X = As(III), 1; Sb(III), 2) were synthesized in aqueous acidic medium by reaction of Ga(3+) ions with the trilacunary, lone-pair-containing [XW9O33](9-). Polyanions 1 and 2 are isostructural and crystallized as the hydrated sodium salts Na6[Ga4(H2O)10(β-AsW9O33)2]·28H2O (Na-1) and Na6[Ga4(H2O)10(β-SbW9O33)2]·30H2O (Na-2) in the monoclinic space group P21/c, with unit cell parameters a = 16.0218(12) Å, b = 15.2044(10) Å, c = 20.0821(12) Å, and β = 95.82(0)°, as well as a = 16.0912(5) Å, b = 15.2178(5) Å, c = 20.1047(5) Å, and β = 96.2(0)°, respectively. The corresponding tellurium(IV) derivative [Ga4(H2O)10(β-TeW9O33)2](4-) (3) was also prepared, by direct reaction of sodium tungstate, tellurium(IV) oxide, and gallium nitrate. Polyanion 3 crystallized as the mixed rubidium/sodium salt Rb2Na2[Ga4(H2O)10(β-TeW9O33)2]·28H2O (RbNa-3) in the triclinic space group P1̅ with unit cell parameters a = 12.5629(15) Å, b = 13.2208(18) Å, c = 15.474(2) Å, α = 80.52(1)°, β = 84.37(1)°, and γ = 65.83(1)°. All polyanions 1-3 were characterized in the solid state by single-crystal XRD, FT-IR, TGA, and elemental analysis, and polyanion 2 was also characterized in solution by (183)W NMR and UV-vis spectroscopy. Polyanion 2 was used as a homogeneous catalyst toward adenosine triphosphate (ATP) and the DNA model substrate 4-nitrophenylphosphate, monitored by (1)H and (31)P NMR spectroscopy. The encapsulated gallium(III) centers in 2 promote the Lewis acidic synergistic activation of the hydrolysis of ATP and DNA model substrates at a higher rate in near-physiological conditions. A strong interaction of 2 with the P-O bond of ATP was evidenced by changes in chemical shift values and line broadening of the (31)P nucleus in ATP upon addition of the polyanion.

Cyclic Tungstoselenites Based on {Se2W12} Units. -Compounds (III) and (V) are characterized by single crystal XRD, 77 Se NMR, FTIR, and Raman spectroscopy. (III) contains the novel macrocyclic anion [{(Se2W12O46)WO(H2O)}3] 24consisting of three Se2W12 fragments, which are connected via three WO(H2O) 4+ groups. The same Se2W12 building block is present in the structure of (V). The hydration numbers of (III) and (V) determined by XRD differ from those determined by thermal and elemental analysis. Na 24 [H 6 Se 6 W 39 O 144 ]·61.25H 2 O and K 2 Na 22 [H 6 Se 6 W 39 O 144 ]·57.75H 2 O (obtained by introduction of some KCl into the mother liquor) crystallize in the triclinic space group P1 with Z = 2. Na13[{Mn2Cl(H2O)2}{Mn(H2O)2}2 (Se2W12O46)2(SeO)2]·51H2O crystallizes in P1 with Z = 1. -(KALININA*, I. V.; PERESYPKINA, E. V.; IZAROVA, N. V.; NKALA, F. M.; KORTZ, U.; KOMPANKOV, N. B.; MOROZ, N. K.; SOKOLOV, M. N.; Inorg. Chem. 53 (2014) 4, 2076-2082, http://dx.