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- W2004154144 abstract "During our studies on the photochemistry of polyoxometalates we have found that the polyoxometalates are potential photosensitizers and electron relay species in redox cycles for chemical conversion of light energy. This paper describes the characterization of multi-electron reduction sites in [Mo8O26(MoO4)2]8− and [Mo7O24]6−, based on the analysis of ESR spectra for UV-irradiated [NH3Me]8[Mo8O26(MoO4)2] · 2H2O and [NH3Pri]6[Mo7O24] · 3H2O single crystals. The ESR spectra show the formation of two distinct localized Mo(V)O5(OH) sites in the lattice. The analysis of the ESR parameters g,95,97 Mo hyperfine structure, and 1H superhyperfine structure indicates the direct participation of H1s in the half-occupied molecular orbital. From the direction of the maximum principal value of the 1H superhyperfine tensor, which lies close to the Mo(V) … H+(O) direction, two paramagnetic sites in the anion can be determined. The results show that the multi-electron photoreduction consists of separate and independent one-electron reductions at four and two octahedral sites in [Mo8O26(MoO4)2]8− and [Mo7O24]6−, respectively. On the other hand, a single crystal of [NH2Pri2]4[H1.5W10O32] · 8H2O, which was a photochemically 1.5-electron reduced species, exhibits extensive delocalization of the paramagnetic electron (around g = 1.84) interacting with eight equivalent hydrogen-bonding protons." @default.
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- W2004154144 date "1986-01-01" @default.
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- W2004154144 title "Multi-electron reduction sites of polymolybdates as photoredox catalysts" @default.
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- W2004154144 doi "https://doi.org/10.1016/s0277-5387(00)84890-1" @default.
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