Construction of Metalloporphyrins Blocked by Fluorine Groups and Evaluation of Their Oxygen-carrying and -activating Ability

通过邻氨基苯基取代的卟啉与相应的全氟烷基羧酸卤化物反应，合成了线形和环状的全氟烷基卟啉。有趣的是，与六氟戊二酰氯、双官能酸氯化物反应生成了亚胺-环状卟啉。分离得到了顺式和反式阿托洛异构体，并用光谱数据进行了表征。将氯化铁引入到反式全氟烷基化的卟啉中很容易与氯化铁发生一锅反应，类似的引入顺式的反应非常缓慢，因此开发了另一种通过氧化二聚体合成的路线。人们试图将这样得到的氯化铁还原为相应的卟啉铁(II)，预计它具有很大的亲氧性，但没有完全转化。在对所获得的卟啉的光谱表征的持续研究中，注意到了卟啉的有趣的光致变色现象。研究发现，光致变色是由于溶剂光降解产生的氯化氢的开关引起的。考察了溶剂、卟啉取代基、光致变色波长对光致变色性的影响。

Linear and Cyclic perfluoroalkylated porphyrins were synthesized by the reactions of o-aminophenyl substituted porphyrins and the corresponding perfluoroalkylated carboxylic acid halides. It is of interest that the reaction with hexafluoroglutaryl chloride, bifunctional carboxylic acid chloride, produced imide-cyclic porphyrin. Atropisomers (cis and trans) were respectively isolated and characterized by spectroscopic data. Introduction of iron (III) chloride into trans-perfluoroalkylated porphyrins was easily performed by one pot reaction with iron (II) chloride and the similar introduction into cis-ones was so sluggish that other synthetic route via mu-oxodimer was developed.Reduction of thus-obtained porphyrin iron (III) chloride to the corresponding porphyrin iron (II), which is expected to be large oxygen affinity, was attempted but full conversion was not recognized. That is still remaining problem to be resolved.In a continuing investigation of spectroscopic characterization of the obtained porphyrins, an interesting photochromism of the porphyrins was noticed. It was found that the photochromism was caused by putting on and off hydrogen chloride, which is generated by photodegradation of solvent. The effects of solvent, porphyrin substituent, and wavelength of photoirradiation on the photochromism were made clear.