含氮芳氧基取代酞菁金属配合物光敏产生^1O2

Photo-generating Singlet Oxygen by Metallophthalocyanines Substituted with Aromaticoxy Group Containing Nitrogen

采用以2,5-二甲基呋喃(DMFU)为探针,通过气相色谱内标法测定了4种中心金属(Zn(Ⅱ)、Cu(Ⅱ)、Ni(Ⅱ)、Co(Ⅱ))、4种取代基及α位或β位取代的28种含氮芳氧基取代酞菁金属配合物新物种光敏产生单线态氧(1O2)的速率常数。讨论了中心金属电子结构、取代基类型及取代位置对酞菁金属配合物光敏产生1O2能力的影响。结果表明,它们产生1O2的能力有很大差异:(1)相同取代基在相同位置取代情况下,中心金属为锌的酞菁配合物光敏产生1O2的能力均好于中心金属为铜、钴、镍的酞菁配合物;(2)氮杂芳氧基取代酞菁锌光敏产生1O2的速率常数显著大于相应位置氨基苯氧基取代酞菁锌的;(3)α位氮杂芳氧基取代酞菁锌光敏产生1O2的速率常数均大于相应取代基β位取代酞菁锌的。

Rate constants of photo-generating singlet oxygen（^1O2） by 28 new metallophthal-ocyanines with center metal Zn（ Ⅱ ）, Cu （ Ⅱ ）, Ni （Ⅱ ） or Co （ Ⅱ ） and with 4 kinds of substituted aromaticoxyl groups containing nitrogen were determined in the presence of 2,5-dimethylfuran （DMFU） as the ^1O2 quencher by GC. The influence of the electron structure of the center metal, the type of the substituent group, and substitution position on the photo-generation of ^1O2 by the metallophthalocyanines were discussed. The results show that （ 1 ）for different metallophthalocyanies with the same subsituent group and the same substitution position, photo-generation of singlet oxygen（ ^1O2 ） by the phthalocyaninatozinc, was more than that of the phthalocyaninatocopper, phthalocyaninatocobalt and phthalocyaninatonickel. （2） the rate constants of photo-generating ^1O2 by the phthalocyaninatozinc substituted with azoaromaticoxy group were obviously higher than that for the phthalocyaninatozinc substituted with aromaticoxy containning amine group. （3） the rate constant of photogenerating ^1O2 by the phthalocyaninatozinc substituted with azoaromaticoxy group at the a position was higher than that with β position substitution.