摘要
以丙酸、乙酸、硝基苯为溶剂一步法合成了四-(二甲氨基苯基)卟啉(T(DMAP)P),并采用氯仿-N,N二甲基甲酰胺为溶剂合成了其与Zn2+,Mn2+,Tb3+三种离子的配合物,考察了溶剂种类、温度、时间对反应的影响,探讨了卟啉与金属盐反应两者用量的最佳比例,在较温和条件下合成了卟啉金属配合物,避免了高温合成金属卟啉不稳定现象。利用元素分析,IR,UV-Vis等方法确定了目标化合物的组成和结构。考察了不同浓度及温度下卟啉配合物的电导率并计算了其摩尔电导率。实验结果发现,卟啉与铽离子配合物摩尔电导率远大于锌、锰配合物。实验研究了不同金属离子对反应的影响,重点考察了卟啉及其金属配合物的分子光谱性能的差异。与四苯基卟啉相比,T(DMAP)P及其金属配合物UV-Vis光谱均发生红移,探讨了该现象产生的原因。
Porphyrin and metalloporphyrin distribute widely in nature and they play an important role in the life. Synthesis of porphyrin compounds with special function has been the focus of attention. In the present paper, porphyrin and metalloporphyrin compound were synthesized by the following method： by one-step synthesis, tetra-（dimethylaminophenyl） porphyrin（T（DMAP） P） was synthesized with propionic acid, acetic acid and nitrobenzene as solvent and 4-dimethylaminobenzaldehyde and pyrrole as raw material. The yield was 24. 24%. The complexes of T（DMAP）P with Zn^2＋, Mn^2＋ and Tb^3＋ were synthesized by solvent of chloroform-N, N dimethylformamide（1 ：1）. The effects of solvent, temperature and reaction time on the reaction were discussed. Optimum proportion between porphyrin and metallic salts was studied also and the molar ratios of T（DMAP）P to Zn （CH3COO）2·2H2O, T（DMAP）P to MnCl2·4H2O, and T（DMAP）P to TbCl3 were 1：1.2,1：1.4, 1：1.5, respectively. The synthesis of metalloporphyrins under mild conditions is simper with high yield （94. 2%, 91.7% and 90.5% for T（DMAP） P combined with Zn^2＋ , Mn^2＋ and Tb^3＋ respectively） and the unstability of metalloporphyrin could be avoided. The constitution and structures of these compounds were studied by elemental analyses, infrared spectrum （IR）, and ultraviolet-visible spectrum （UV-Vis）. The conductivity of porphyrin compound with different concentration and temperature was studied. It was found that the molar conductivity of T（DMAP）P-TbCl（74. 6 s·cm^-2·mol^-1） was greater than that of T（DMAP）P-Zn （8.8 s·cm^-2·mol^-1） and T（DMAP）P-Mn （25.8 s·cm^-2·mol^-1 ）. So T（DMAP）P-TbCl could be regarded as the 1 ： 1 electrolyte compound while T（DMAP）P-Zn and T（DMAP）P-Mn were non-electrolyte compounds. The influences of different metal ions on the reaction were investigated. The discussion was concentrated on the molecular spectra of porphyrin and metalloporphyrin. Compared wit
出处
《光谱学与光谱分析》
SCIE
EI
CAS
CSCD
北大核心
2007年第12期2566-2569,共4页
Spectroscopy and Spectral Analysis
基金
国家自然科学基金项目(20577016)
山东省重点学科基金项目(XTD0705)资助
关键词
卟啉
金属卟啉
合成
结构表征
光谱性能
Porphyrin
Metalloporphyrin
Synthesis
Structure characterization
Spectroscopic property
