Synthesis and characterization of multinuclear manganese-containing tungstosilicates

The five manganese-containing, Keggin-based tungstosilicates [Mn(II)3(OH)3(H2O)3(A-α-SiW9O34)](7-) (1), [Mn(III)3(OH)3(H2O)3(A-α-SiW9O34)](4-) (2), [Mn(III)3(OH)3(H2O)3(A-β-SiW9O34)](4-) (3), [Mn(III)3Mn(IV)O3(CH3COO)3(A-α-SiW9O34)](6-) (4), and [Mn(III)3Mn(IV)O3(CH3COO)3(A-β-SiW9O34)](6-) (5) were synthesized in aqueous medium by interaction of [A-α-SiW9O34](10-) or [A-β-SiW9O34H](9-) with either MnCl2 (1) or [Mn(III)8Mn(IV)4O12(CH3COO)16(H2O)4] (2-5) under carefully adjusted reaction conditions. The obtained salts of these polyanions were analyzed in the solid state by single-crystal X-ray diffraction, IR spectroscopy, and thermogravimetric analysis. The salts of polyanions 1, 2, and 4 were further characterized in the solid state by magnetic studies, as well as in solution by electrochemistry.