【摘要】 合成了系列取代铁卟啉化合物,研究了拉曼光谱及红外光谱。对二价铁卟啉RTPPFe(Ⅱ)和三价铁卟啉RTPPFeCl(Ⅲ)的红外光谱和拉曼光谱进行了对比分析,结果表明,二价铁卟啉在常温下是不稳定的,通常在其轴向位置上吸附氧分子而形成铁卟啉的超氧化物RTPPFe-O2,其稳定的立体构型为end-on式结构。采用量化软件对化合物的分子结构进行了模拟,得出了其分子结构参数,并结合化合物的红外及拉曼光谱,研究了分子结构对波谱位移的影响。不同结构的二价铁卟啉RTPPFe-O2拉曼及红外吸收峰的位置发生了不同程度的位移,其位移情况与分子的扭曲程度有关,即RTPPFe-O2的Fe-O2特征拉曼吸收峰以及红外特征吸收峰(Fe—O)的位置随着Fe—O—O角的增大而向高波数移动。更多还原

【Abstract】 In the present paper,two series of substituted tetraphenylporphyrin iron compounds RTPPFe(Ⅱ) and RTPPFeCI(Ⅲ) were synthesized by two-step synthetic method.Raman and IR spectra of tetraphenylporphyrin iron complexes were investigated.By analyzing the IR and Raman spectra of RTPPFe(Ⅱ) and RTPPFe(Ⅲ)Cl,it was confirmed that the RTPPFe(Ⅱ) complexes were usually unstable at normal temperature and existed via the coordination of dioxygen with the iron(Ⅱ) center,i.e.they formed into TPPFe-O2,and the stable configuration of dioxygen with the iron(Ⅱ) center was "end-on".In addition,the geometric structure optimization of substituted iron tetraphenylporphyrin complexes was performed by PM3 semi-empirical and MM+ method quantum calculation.The structure parameters were obtained,including EHOMO,ELUMO and total energy,bond length of Fe—Cl etc.The effect of molecular structure on vibrational frequency shift was studied by combing the IR and Raman spectra.The results showed that for iron tetraphenylporphyrins(RTPPFe-O2) with different structure,the vibrational frequencies of the Fe—O bond were associated with their twist degree of molecular structures,i.e.the Raman and IR characterization vibrational frequencies of the Fe—O2 were up shifted with the increase in the Fe—O—O angle of iron tetraphenylporphyrins(RTPPFe-O2) molecule.更多还原