β-硝基和β-氨基取代卟啉的合成及光谱分析

发布时间：2018-07-08 16:03

本文选题：β-硝基- + -四苯基卟啉　；参考：《精细化工》2017年05期

【摘要】：以5,10,15,20-四苯基卟啉(TPP)为原料,用硝酸铜硝化法合成了β-NO_2-TPP及其铜配合物(β-NO_2-CuTPP),经还原反应制备了β-NH_2-TPP及其铜配合物(β-NH_2-CuTPP)。当n(Cu-TPP)∶n[Cu(NO3)2]=1∶1时,40℃下,β-NO_2-CuTPP的产率为83.2%;当n(SnCl_2)∶n(β-NO_2-TPP)=1∶1时,65℃下,β-NH_2-TPP的产率为68.0%。通过MS、1HNMR、UV-Vis和IR对所合成化合物进行了表征,考察了其紫外和荧光光谱性质。结果表明:与TPP相比,UV-Vis光谱中,β-NO_2-TPP、β-NH_2-TPP、β-NO_2-CuTPP和β-NH_2-CuTPP的Q带吸收峰有4~19nm的红移;荧光光谱中,相对于TPP,β-NH_2-TPP的最大发射峰红移了4 nm,β-NO_2-TPP的两个发射峰则分别红移1 nm和蓝移27 nm,β-NO_2-CuTPP和β-NH_2-CuTPP发生了荧光淬灭;当溶剂从甲苯变为二氯甲烷、氯仿和乙腈时,β-NH_2-TPP的荧光发射波长从656 nm变为655、656和654 nm,相对于溶剂极性的增大,未显示出明显的变化。但β-NH_2-TPP的荧光量子产率则从0.359 7增加到了0.668 1,0.719 0和1.084 7。卟啉化合物产生单线态氧降解1,3-二苯基异苯并呋喃(DPBF)实验结果表明:在25 min时,β-NH_2-TPP和TPP使DPBF的降解率分别达到了27%和23%,说明β-NH_2-TPP产生单线态氧的能力明显优于TPP。
[Abstract]:尾 -NO _ 2-TPP and its copper complex (尾 -no _ 2-CuTPP) were synthesized by nitration of copper nitrate from 5o _ (10) 10 ~ (15) ~ (15) ~ (15) -tetraphenyl porphyrin (TPP). 尾 -NH _ 2-TPP and its copper complex (尾 -NH _ 2-CuTPP) were prepared by reducing reaction. When n (Cu-TPP): n [Cu (No3) 2] 1: 1, the yield of 尾 -NO2-CuTPP is 83.2 and when n (SnCl2): n (尾 -NO2-TPP) 1: 1, the yield of 尾 -NH2-TPP is 68.0. The synthesized compounds were characterized by MS 1HN MR-UV-Vis and IR, and their UV and fluorescence spectra were investigated. The results show that the Q-band absorption peaks of 尾 -NOS _ 2-TPP, 尾 -NH _ 2-TPP, 尾 -no _ 2-CuTPP and 尾 -NH _ 2-CuTPP have red shift of 4~19nm, the maximum emission peak of 尾 -NH _ 2-TPP shifts 4 nm in comparison with 4~19nm, and the two emission peaks of 尾 -no _ 2-TPP shift 1 nm and blue shift 27 nm, 尾 -NO _ 2-CuTPP and 尾 -NH _ 2-CuTPP have fluorescence quenching, respectively, compared with TPP, the maximum emission peak of 尾 -NH2-TPP shifts to 4 nm, and the two emission peaks of 尾 -NO2-TPP are red-shifted to 1 nm and blue shift to 27 nm, 尾 -NO2-CuTPP and 尾 -NH2-CuTPP occur fluorescence quenching. When the solvent changed from toluene to dichloromethane, chloroform and acetonitrile, the fluorescence emission wavelength of 尾 -NH2-TPP changed from 656nm to 655656 and 654nm, which showed no obvious change compared with the increase of solvent polarity. However, the fluorescence quantum yields of 尾 -NH2-TPP increased from 0.359 7 to 0.668 1D 0.719 0 and 1.084 7. The results showed that 尾 -NH2-TPP and TPP resulted in the degradation rate of DPBF by 27% and 23% respectively at 25 min, indicating that 尾 -NH2-TPP is superior to TPPin in generating singlet oxygen.
【作者单位】：武汉工程大学化学与环境工程学院;武汉工程大学化工与制药学院;
【基金】：国家自然科学基金(20471045)~~
【分类号】：O626;O657.3

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