含吡唑、四氮唑基卟啉及卟淋配合物的合成、表征及性能研究

发布时间：2018-06-13 08:02

  本文选题：卟啉 + 金属卟啉配合物　； 参考：《西北大学》2016年硕士论文

【摘要】：卟啉及金属卟啉化合物广泛地存在于自然界的生命体系中,在很多生命体中具有重要的作用。基于卟啉和金属卟啉的特殊性能,合成新的卟啉、构筑其金属卟啉配合物,研究它们的催化氧化性能,对于进一步深入理解含金属卟啉酶的催化机理,以及它们今后的实际应用都有很重要的意义。论文以中位取代的含吡唑基、四氮唑基的卟啉为配体,研究了它们与金属离子构筑的金属卟啉配合物,并对得到的卟啉配合物进行了光谱、结构及催化性能表征。主要内容有：1.采用不同的路线合成了三种自由卟啉,包括5,10,15,20-四-(4-吡唑基)苯基卟啉(H2Ppl),5,15-二-(叔丁基)-10,20-二-(4-吡唑基)苯基卟啉(H2Pp2)和5,10,15,20-四-[4-(2,3,4,5)-四氮唑基]苯基卟啉(H2Pp3),对所合成的三种自由卟啉进行了质谱(MS)、核磁(1HNMR)、紫外-可见(UV-vis)、元素分析(EA)以及傅里叶变换红外光谱(FT-IR)表征,相关的表征证实了所合成的三种自由卟啉与所设计的分子结构相一致。2.以自由卟啉H2Pp1和H2Pp2为构筑单元和过渡金属盐(Co2+、Ni2+、Cu2+、Zn2+和Mn2+)通过溶剂热法制备得到了五种金属卟啉配合物(CoPp1、CuPp1、MnPp、ZnPp1和NiPp2),对其中H2Pp1、CoPp1、CuPp1、 MnPp和NiPp2的单晶结构进行了分析,并对所合成的配合物进行了UV-Vis、FT-IR、TGA、XRD、EA及荧光光谱表征。TGA表明配合物在400℃以下均具有稳定的结构。研究了卟啉配合物对芳香烷烃的催化氧化活性,结果表明,CoPp1和MnPp1具有高的催化活性。3.以中位取代的四氮唑基卟啉H2Pp3为基本的构筑单元和金属盐(Fe3+、Co2+、Ni2+、 Cu2+、Zn2+、Mn2+和Pb2+通过溶剂热法制备得到了7个配位聚合物(Fe-Pp3、Co-Pp3、 Ni-Pp3、Cu-Pp3、Zn-Pp3、Mn-Pp3和Pb-Pp3),对它们进行了FT-IR、UV-Vis、粉末XRD、TGA、扫描电镜和氮气吸附等性能表征。热重曲线表明这些配位聚合物在380℃C以下均具有稳定的结构,SEM表明这些配位聚合物具有球状的形貌,BET比表面积在40.3-95.4m2·g-1之间。多相催化实验表明,Fe-Pp3、Co-Pp3、Cu-Pp3和Mn-Pp3对芳香烷烃具有较高的的催化氧化活性,催化剂循环使用3次后仍可以保持较高的催化活性。
[Abstract]:Porphyrins and metalloporphyrins widely exist in natural life systems and play an important role in many living organisms. Based on the special properties of porphyrins and metalloporphyrins, new porphyrins were synthesized, their metalloporphyrin complexes were constructed and their catalytic oxidation properties were studied. And their future practical applications are of great significance. In this paper, the metalloporphyrin complexes with pyrazolyl and tetrazolyl as ligands were studied, and the spectra, structures and catalytic properties of the obtained porphyrin complexes were characterized. The main content is: 1. Three kinds of free porphyrin were synthesized by different routes. H2Pp3 porphyrin H2Pp3H2Pp3 was prepared by mass spectrometry of three kinds of free prophyrins, H2Pp2 (Tertiary Ding Ji (tertiary Ding Ji), 20- di-4-pyrazolyl) phenyl porphyrin (H2Pp2), and 510101520- [4-2334- tetrazolyl] phenyl porphyrin (H2Pp3H2Pp3H2Pp3H), respectively. The H2Pp3H2Pp3H2Pp3H2Pp3 porphyrin was prepared by mass spectrometric analysis of the three kinds of free prophyrins, 1HNMRs, 1HNMRs, UV-visible porphyrins (H2Pp2Pp2Pp2Pp2Pp2Pp2Pp2Pp2). UV-VIS, elemental analysis (EAA) and Fourier transform infrared spectroscopy (FTIR) characterization, The related characterization confirmed that the three kinds of free porphyrin synthesized were consistent with the designed molecular structure. 2. Five kinds of metalloporphyrin complexes (CoPp1CuP1MnPp1 and NiP1MnPp1) were prepared by solvothermal method using free porphyrin H2Pp1 and H2Pp2 as building units and transition metal salts Co2P1, MnPp1 and MnPp2. The single crystal structures of H2Pp1CoP1, MnPp and NiPp2 were analyzed. The synthesized complexes were characterized by UV-Vis-FT-IRGA-XRDEA and fluorescence spectra. The results show that the complexes have stable structures below 400 鈩，

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