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A new Zr-substituted polyoxometalate(POM) [(CH_3)_4N]_6H_2Cs_2(H_2O)_4[Zr_2(μ2-OH)_2(α-SiW_(11)O_(39))_2]·27H_2O(1) was prepared by the reaction of K_(10)[A-α-SiW_9O_(34)]·25H_2O with ZrCl_4 in 0.5 mol/L NaAc-HAc(Ac = CH_3COO~-) buffer solution(pH = 4.5). 1 was characterized by elemental and thermogravimetric analyses, powder X-ray diffraction and single-crystal X-ray diffraction. The title compound crystallizes in monoclinic system, space group P2_(1/m) with a = 13.1865(16), b = 20.964(3), c = 21.432(3) ?, V = 5923.9(12) ?~3, Z = 2, D_c = 3.833 mg/m~3, μ = 22.175 mm~(-1), F(000) = 6116, the final R = 0.0697 and wR = 0.1959 for 10319 observed reflections with I > 2σ(I). Single-crystal X-ray structure analysis reveals that 1 exhibits a one-dimensional chain structure based on sandwiched-type POM anions [Zr_2(μ2-OH)_2(α-SiW_(11)O_(39))_2]~(10-) linked by Cs+cations. In addition, catalytic tests indicate that 1 provides a sufficient driving force for the conversion from thioethers to sulfoxides/sulfones by H_2O_2.
A new Zr-substituted polyoxometalate (POM) [(CH_3) _4N] _6H_2Cs_2 (H_2O) _4 [Zr_2 (μ 2 -OH) _2 (α-SiW_ (11) O_ (39)) _ 2] · 27H_2O the reaction of K_ (10) [A-α-SiW_9O_ (34)] · 25H_2O with ZrCl_4 in 0.5 mol / L NaAc-HAc buffer solution The title compound crystallizes in a monoclinic system, space group P2_ (1 / m) with a = 13.1865 (16), b = 20.964 (3), c = 21.432 (3) ?, V = 5923.9 (12)? ~ 3, Z = 2, D_c = 3.833 mg / m 3 and μ = 22.175 mm -1, F (000) = 6116 and the final R = 0.0697 and wR = 0.1959 for 10319 observed reflections with I> 2σ (I). Single-crystal X-ray structure analysis reveals that 1 exhibits a one-dimensional chain structure based on sandwiched-type POM anions [Zr 2 (μ 2 -OH) (α-SiW_ (11) O_ (39)) _2] ~ (10-) linked by Cs + cations. In addition, catalytic tests indicate that 1 provides a sufficient driving force for the conversion from thioether s to sulfoxides / sulfones by H_2O_2.