A One-Dimensional Chain of Manganese(ii) Bridged Peroxomolybdate Isolated from an Aqueous Mn-polymolybdate-H2O2 System.

A new manganese(II)-peroxomolybdate complex, Cs4[Mn(OH2)2(Mo7O22(O2)2)]·4.25H2O (Cs-1), was isolated from an aqueous solution containing manganese(II) sulfate, sodium heptamolybdate and hydrogen peroxide by the addition of Cs+ salt. Cs-1 was characterized by single crystal X-ray diffraction, thermogravimetry (TG), IR spectroscopy, powder X-ray diffraction (PXRD), cyclic voltammetry (CV) and ultraviolet-visible spectroscopy (UV-vis). The diperoxoheptamolybdate [Mo7O22(O2)2]6- units were linked by Mn(II) ions to form a one-dimensional infinite chain of [Mn(OH2)2(Mo7O22(O2)2)]n4n-, which represents a unique structure with the coexistence of the oxidant-reductant pair O22-/Mn2+. The interconversion between [MnII(OH2)2(Mo7O22(O2)2)]4- and [MnMo9O32]6- in the aqueous solution was monitored by UV-vis spectrophotometry. It indicates that 1 is a key intermediate during the redox cycle of Mn(II) and Mn(IV) in the Mn-polyoxometalate-H2O2 system. In the oxidation process of 3,3',5,5'-tetramethylbenzidine and ortho-phenylenediamine by H2O2, Cs-1 shows notable activity as an enzyme mimetic catalyst.