β-硝基和β-氨基取代卟啉的合成及光谱分析  

Synthesis and Spectroscopic Properties of β-Nitro-substituted and β-Amino-substituted Tetraphenylporphyrins

作　　者：王慧东[1] 陈楚珺 冯瑾瑾 黄齐茂[2] 高洪[1] 

机构地区：[1]武汉工程大学化学与环境工程学院,湖北武汉430073 [2]武汉工程大学化工与制药学院,湖北武汉430073

出　　处：《精细化工》2017年第5期525-531,587,共8页Fine Chemicals

基　　金：国家自然科学基金(20471045)~~

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。β-NO2-TPP and its copper complex （ β-NO2-CuTPP） were synthesized by selective nitration of metal salts, using 5,10,15,20-tetraphenylporphyrin （TPP） as raw material. Subsequently, β-NH2- TPP and its copper complex （β-NHz-CuTPP） were prepared by reduction of β-NOE-TPP. When n（Cu- TPP） ： n [ Cu （ NO3 ） 2 ]was 1 ： 1, the yield of β-NO2-CuTPP was 83.2% at 40℃. When n （ SnC12 ） ： n （ β- NO2-TPP） was 1 ： 1, the yield of β-NHE-TPP was 68.0% at 65 ~C. The structure of the synthesized compounds was characterized by MS,1HNMR, UV-Vis and IR. The UV-Vis and fluorescence spectra properties were investigated. The results showed that compared with TPP, the absorption peaks of Q- bands for β-NO2-TPP,β-NH2-TPP,β-NO2-CuTPP and β-NH2-CuTPP produced red shifts from 4 to 19 nm in UV-Vis spectra. In the fluorescence spectra, the maximum emission peak with a red shift 4 nm was observed for β-NH2-TPP, and red shiift 1 nm, blue shift 27 nm of the emission peak was observed for β-NO2-TPP. However, β-NO2-CuTPP and β-NHE-CuTPP exhibited fluorescence quenching phenomena. In addition,the fluorescence emission wavelength of fl-NHz-TPP appeared at 656 nm,655 nm ,656 nm and 654 nm in toluene ,chloroform, dichloromethane and acetonitrile ,which did not exhibit obvious change with the increase of solvent polarity. But the fluorescence quantum yield of β-NH2-TPP increased from 0. 359 7 to 0. 668 1,0. 719 0 and 1. 084 7. Meanwhile,and these compounds was used to degrade 1,3-diphenylisobenzofuran （DPBF）. As a result, the degradation rate of DPBF by β-NH2- TPP reaehed to 27% at the time of 25 min, which indicated that β-NH2-TPP showed better ability to produee singlet oxygen than TPP.

关 键 词：β-硝基-5 10 15 20-四苯基卟啉 β-氨基-5 10 15 20-四苯基卟啉 光谱性质 功能材料 

分 类 号：O626.13[理学—有机化学]