Defect {(WVIO7)WVI4} and Full {(WVIO7)WVI5} Pentagonal Units as Synthons for the Generation of Nanosized Main Group V Heteropolyoxotungstates

Abstract

We report on the synthesis and characterization of three new nanosized main group V heteropolyoxotungstates K_xNa_y[H₂(XW^VI₉O₃₃)(W^VI₅O₁₂)(X₂W^VI₂₉O₁₀₃)]·nH₂O {X₃W₄₃} (x = 11, y = 16, and n = 115.5 for X = Sb^III; x = 20, y = 7, and n = 68 for X = Bi^III) and K₈Na₁₅[H₁₆(Co^II(H₂O)₂)_0.9(Co^II(H₂O)₃)₂(W^VI_3.1O₁₄)(Sb^IIIW^VI₉O₃₃)(Sb^III₂W^VI₃₀O₁₀₆)(H₂O)]·53H₂O {Co₃Sb₃W₄₂}. On the basis of the key parameters for the one-pot synthesis strategy of {Bi₃W₄₃}, a rational step-by-step approach was developed using the known Krebs-type polyoxotungstate (POT) K₁₂[Sb^V₂W^VI₂₂O₇₄(OH)₂]·27H₂O {Sb₂W₂₂} as a nonlacunary precursor leading to the synthesis and characterization of {Sb₃W₄₃} and {Co₃Sb₃W₄₂}. Solid-state characterization of the three new representatives {Bi₃W₄₃}, {Sb₃W₄₃}, and {Co₃Sb₃W₄₂} by single-crystal and powder X-ray diffraction (XRD), IR spectroscopy, thermogravimetric analysis (TGA), energy-dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS), and elemental analysis, along with characterization in solution by UV/vis spectroscopy shows that {Bi₃W₄₃}, {Sb₃W₄₃}, and {Co₃Sb₃W₄₂} represent the first main group V heteropolyoxotungstates encapsulating a defect {(W^VIO₇)W^VI₄} ({X₃W₄₃}, X = Bi^III and Sb^III) or full {(W^VIO₇)W^VI₅} ({Co₃Sb₃W₄₂}) pentagonal unit. With 43 tungsten metal centers, {X₃W₄₃} (X = Bi^III and Sb^III) are the largest unsubstituted tungstoantimonate- and bismuthate clusters reported to date. By using time-dependent UV/vis spectroscopy, the isostructural representatives {Sb₃W₄₃} and {Bi₃W₄₃} were subjected to a comprehensive study on their catalytic properties as homogeneous electron-transfer catalysts for the reduction of K₃[Fe^III(CN)₆] as a model substrate revealing up to 5.8 times higher substrate conversions in the first 240 min (35% for {Sb₃W₄₃}, 29% for {Bi₃W₄₃}) as compared to the uncatalyzed reaction (<6% without catalyst after 240 min) under otherwise identical conditions.