Institute of Green Chemistry and Fine Chemicals, Beijing University of Technology, Beijing 100124, China.
Molecules. 2011 Apr 6;16(4):2960-70. doi: 10.3390/molecules16042960.
A series of substituted tetraphenylporphyrin iron chloride complexes [RTPPFe(III)Cl, R=o/p-NO₂, o/p-Cl, H, o/p-CH₃, o/p-OCH₃] were synthesized by a novel universal mixed-solvent method and the spectral properties of free base porphyrins and iron porphyrin compounds were compared with each other. The experimental results showed that the one-pot mixed solvent method was superior to the two-step method in the yields, reaction time and workup of reaction mixtures for the synthesis of iron porphyrin compounds. The highest yields (28.7%-40.4%) of RTPPFe(III)Cl were obtained in the mixed solvents propionic acid, glacial acetic acid and m-nitrotoluene under reflux for 2 h. A detailed analysis of ultraviolet-visible (UV-vis), infrared (IR) and far-infrared (FIR) spectra suggested the transformation from free base porphyrins to iron porphyrins. The red shift of the Soret band in ultraviolet-visible spectra due to the presence of p-nitrophenyl substituents and the blue shift of Fe-Cl bond of TPPFeCl in far-infrared spectra were further explained by the electron transfer and molecular planarity in the porphyrin ring.
一系列取代的四苯基卟啉铁氯化物配合物[RTPPFe(III)Cl，R=邻/对-NO₂，邻/对-Cl，H，邻/对-CH₃，邻/对-OCH₃]通过一种新的通用混合溶剂法合成，并比较了游离基卟啉和铁卟啉化合物的光谱性质。实验结果表明，一锅混合溶剂法在产率、反应时间和反应混合物的后处理方面优于两步法，用于合成铁卟啉化合物。在回流 2 小时的丙酸、冰醋酸和间硝基甲苯混合溶剂中，RTPPFe(III)Cl 的产率最高（28.7%-40.4%）。对紫外可见（UV-vis）、红外（IR）和远红外（FIR）光谱的详细分析表明了从游离基卟啉到铁卟啉的转变。由于存在对硝基苯基取代基，紫外可见光谱中 Soret 带的红移和远红外光谱中 TPPFeCl 的 Fe-Cl 键的蓝移进一步解释了卟啉环中的电子转移和分子平面性。
