The functional core of oxygenic photosynthesis is in charge of catalytic water oxidation by a multi-redox Mn(III)/Mn(IV) manifold that evolves through five electronic states (S(i), where i=0-4). The synthetic model system of this catalytic cycle and of its S0→S4 intermediates is the expected turning point for artificial photosynthesis. The tetramanganese-substituted tungstosilicate [Mn(III)3Mn(IV)O3(CH3COO)3(A-α-SiW9O34)](6-)(Mn4POM) offers an unprecedented mimicry of the natural system in its reduced S0 state; it features a hybrid organic-inorganic coordination sphere and is anchored on a polyoxotungstate. Evidence for its photosynthetic properties when combined with [Ru(bpy)3](2+) and S2O8(2-) is obtained by nanosecond laser flash photolysis; its S0→S1 transition within milliseconds and multiple-hole-accumulating properties were studied. Photocatalytic oxygen evolution is achieved in a buffered medium (pH 5) with a quantum efficiency of 1.7%.
POMs, magnets, and Co: The tetrameric 36‐tungsto‐8‐phosphate [{Co4(OH)3PO4}4(PW9O34)4]28− containing 16 cobalt(II) centers was prepared by a simple, one‐pot synthetic procedure. The {Co16(OH)12(PO4)4}8+ core (see picture) exhibits single‐molecule magnetic behavior.
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