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化学学报
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化学学报 ›› 1996, Vol. 54 ›› Issue (4): 385-391. 上一篇    下一篇

研究论文

金属卟啉化合物光谱化反应研究 Ⅱ. 周边取代与轴向配位对金属卟啉光敏化反应的影响

杨国昱;王清华;张杰;于连香;曹锡章;徐吉庆   

  1. 吉林大学化学系
  • 发布日期:1996-04-15

Studies on the photochemical reactions catalyzed by metalloporphyrin complexes Ⅱ. affect photosensitized reaction by aroundsubstituting group and axial coordination of metalloporphyrin complexes

WANG QINGHUA;ZHANG JIE;YU LIANXIANG;CAO XIZHANG;XU JIQING   

  • Published:1996-04-15

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本文研究了中-四(对三甲胺基苯基)金属卟啉(MeTPI, Me=H2, Zn(Ⅱ),Cu(Ⅱ), Ni(Ⅱ), Mn(Ⅲ), Co(Ⅲ))光敏化还原甲基紫精(MVI2)反应, 用动力学方程参数a, 诱导时间ti和初始反应速率v0来衡量光敏剂的优劣。同时讨论了不同的取代基以及不同的轴向配体对光敏剂光敏性的影响。结果表明: Zn(Ⅱ)TPI的光敏性较好; 含氮芳香有机碱对光敏剂起"增敏"作用, 并且通过引入带有正电荷的轴向配体, 使"增敏"效果更加显著, 同时发现, 脂肪胺起"降敏"作用。

关键词: 光敏化, 锌络合物, 铜络合物, 光催化, 钴络合物, 镍络合物, 甲基紫精, 卟啉, 轴向配位体

The photosensitized reduction reaction of methylviologen was investigated by tetrakis [(4-trimethylamino) phenyl] metalloporphyrins [MeTPI, Me=H2, Zn(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), Mn(Ⅲ), Co(Ⅲ)]. The kinetic parameter a, inductive time ti and initial rate v0 in photosensitized reaction were applied to measure the photosensitivity of photosensitizers. Both substituting groups and axial coordinations of metalloporphyrin can exert a great influence on the photosensitivity of photosensitizers. The experimental results domonstrated that (1) zinc porphyrin is the best photosensitizers in the same series of porphyrins and metalloporphyrins; (2) the aromatic organic bases can increase the photosensitivity through axial ligation, on the contrary, the aliphatic amines can decrease the photosensitivity; (3) the aromatic organic bases with positive charge can increase the photosensitivity considerably.

Key words: PHOTOSENSITIZATION, ZINC COMPLEX, COPPER COMPLEX, PHOTOCATALYSIS, COBALT COMPLEX, NICKEL COMPLEX, METHYL VIOLOGEN, PORPHYRIN, AXIAL LIGANDS

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