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>Phthalocyanines and related macrocycles for multi‐electron transfer in catalysis, photochemistry and photoelectrochemistry
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Phthalocyanines and related macrocycles for multi‐electron transfer in catalysis, photochemistry and photoelectrochemistry
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机译：Phthalocyanines and related macrocycles for multi‐electron transfer in catalysis, photochemistry and photoelectrochemistry
AbstractAt different phthalocyanines and related macrocycles it is shown that one‐step, multi‐electron transfer and one‐step, multi‐change of oxidation states occur. At first, the catalytic oxidations of thiols and sulfide in the presence of different Co(II)phthalocyanines are discussed. Thiolates are oxidized to disulfides via a two‐electron transfer whereas the reduction of O2occurs via a two‐ or four‐electron transfer to H2O2or H2O. Zn(II) and Al(III)phthalocyanines are efficient sensitizers for the conversion of triplet to singlet dioxygen under illumination with visible light. In the presence of thiolates or sulfides an efficient photo‐oxidation to sulfonic acids or sulfate is observed. The oxidation state of sulfur changes from −2 to +4 or +6, respectively. This process of singlet oxygen reactions finds application in the photodynamic therapy of cancer. The unsubstituted zinc(II)‐phthalocyanine as p‐type molecular semiconductor can efficienfly reduce O2in photoelectrochemical experiments whereas zinc(II)phthalocyanines with electronwithdrawing groups as n‐type conductors are active in the photoelectrochemical oxidation of thiols. All processes include multi‐electron transfer. The electrocatalytic reduction of CO2is investigated at electrodes modified with Co(II)phthalocyanine. In particular, the phthalocyanine in a polyvinylpyridine membrane is active, so the CO2is reduced to CO by multi‐electron transfer. In addition, two photon excitations of a Mg(II)phthalocyanine are presented and
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