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采用稳态和时间分辨的瞬态光谱技术对比研究了5种新型Corrole卤族衍生物Corrole-F,Corrole-Cl,Corrole-Br,Corrole-I和Corrole-2I的光物理特性.稳态吸收光谱表明:5种样品的光谱结构基本相同,在420nm附近有一个强吸收峰,对应B带吸收;在450~650nm之间存在较弱的吸收峰,对应Q带吸收.光谱形状与卟啉单体相似,但具有更强的Q带吸收.Corrole-F的吸收强度最小,随着卤素原子序数和原子数量的增加,吸收明显增强.单卤代Corrole-I的吸收明显比双卤代的Corrole-2I强.稳态荧光光谱表明:5种样品的荧光峰均在650nm处,其中Corrole-F的发光强度最强,且随着卤素原子序数和数量的增加,发光强度明显减弱.而单卤代Corrole-I的发光量子产率(0.947%)明显比双卤代Corrole-2I量子产率(0.381%)高.荧光衰变动力学测量结果表明:随着卤素原子序数和数量的增加,Corrole衍生物的荧光寿命变短,而从S1态跃迁到T1态的系间窜跃时间急剧减小,相应的系间窜跃几率迅速增大,这有利于三线态量子产率的提高.最后讨论了重原子效应对光动力学治疗中活性氧产生的影响.
The photophysical properties of five novel Corrole halogen derivatives, Corrole-F, Corrole-Cl, Corrole-Br, Corrole-I and Corrole-2I, were compared using steady state and time resolved transient spectroscopy. The results showed that the spectra of the five samples were basically the same with a strong absorption peak near 420nm corresponding to the absorption of B band and a weak absorption peak from 450nm to 650nm corresponding to absorption of Q band.The spectral shape was similar to that of porphyrin monomer , But with stronger absorption of Q. Corrole-F has the lowest absorption intensity and the absorption is obviously enhanced with the increase of atomic number and atomic number of halogen.The absorption of mono-halo-Corrole-I is obviously higher than that of Corrole- 2I.The steady-state fluorescence spectra show that the fluorescence peaks of the five samples are all at 650nm, of which the luminescence intensity of Corrole-F is the strongest, and the luminescence intensity is obviously weakened with the increase of the number and the number of halogen atoms. The quantum yield of Corrole-I (0.947%) was significantly higher than that of the bis-halo-Corrole-2I (0.381%). The results of the fluorescence decay kinetics showed that with the increase of atomic number and the number of halogen atoms, Of the fluorescence life shorter, and transition from the S1 state to T1 state inter-channeling Time drastically reduced, corresponding intersystem crossing probability increases rapidly, which favors the triplet quantum yield. Finally the effects of the heavy atom effect of photodynamic active oxygen treatment.