The manganese(III)-containing tungstophosphate [MnIII3(H2O)5(A-α-PW9O34)2]9−

Reaction of [MnIII8MnIV4O12(CH3COO)16(H2O)4] with [A-α-PW9O34]9− in a 1:2 molar ratio in aqueous, acidic medium resulted in the manganese(III)-containing, sandwich-type tungstophosphate [MnIII3(H2O)5(A-α-PW9O34)2]9− (1). Polyanion 1 crystallizes as a mixed potassium/cesium/guanidinium salt in the triclinic space group P1¯, with cell parameters a = 13.1718(19) Å, b = 16.505(2) Å, c = 22.842(4) Å, α = 104.141(7)°, β = 106.267(8)°, γ = 101.369(6)°, V = 4430.6(12) Å3, and Z = 2. The title polyanion comprises two [A-α-PW9O34]9− Keggin fragments linked via three MnIII ions, two of which are 6-coordinated and one is 5-coordinated. Polyanion 1 was further characterized by IR, TGA, elemental analysis, magnetic measurements, and electrochemistry.

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