本文選題：卟啉 + 金屬卟啉配合物��； 參考：《西北大學》2016年碩士論文

【摘要】：卟啉及金屬卟啉化合物廣泛地存在于自然界的生命體系中,在很多生命體中具有重要的作用�；谶策徒饘龠策奶厥庑阅�,合成新的卟啉、構(gòu)筑其金屬卟啉配合物,研究它們的催化氧化性能,對于進一步深入理解含金屬卟啉酶的催化機理,以及它們今后的實際應用都有很重要的意義。論文以中位取代的含吡唑基、四氮唑基的卟啉為配體,研究了它們與金屬離子構(gòu)筑的金屬卟啉配合物,并對得到的卟啉配合物進行了光譜、結(jié)構(gòu)及催化性能表征。主要內(nèi)容有：1.采用不同的路線合成了三種自由卟啉,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),對所合成的三種自由卟啉進行了質(zhì)譜(MS)、核磁(1HNMR)、紫外-可見(UV-vis)、元素分析(EA)以及傅里葉變換紅外光譜(FT-IR)表征,相關(guān)的表征證實了所合成的三種自由卟啉與所設計的分子結(jié)構(gòu)相一致。2.以自由卟啉H2Pp1和H2Pp2為構(gòu)筑單元和過渡金屬鹽(Co2+、Ni2+、Cu2+、Zn2+和Mn2+)通過溶劑熱法制備得到了五種金屬卟啉配合物(CoPp1、CuPp1、MnPp、ZnPp1和NiPp2),對其中H2Pp1、CoPp1、CuPp1、 MnPp和NiPp2的單晶結(jié)構(gòu)進行了分析,并對所合成的配合物進行了UV-Vis、FT-IR、TGA、XRD、EA及熒光光譜表征。TGA表明配合物在400℃以下均具有穩(wěn)定的結(jié)構(gòu)。研究了卟啉配合物對芳香烷烴的催化氧化活性,結(jié)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為基本的構(gòu)筑單元和金屬鹽(Fe3+、Co2+、Ni2+、 Cu2+、Zn2+、Mn2+和Pb2+通過溶劑熱法制備得到了7個配位聚合物(Fe-Pp3、Co-Pp3、 Ni-Pp3、Cu-Pp3、Zn-Pp3、Mn-Pp3和Pb-Pp3),對它們進行了FT-IR、UV-Vis、粉末XRD、TGA、掃描電鏡和氮氣吸附等性能表征。熱重曲線表明這些配位聚合物在380℃C以下均具有穩(wěn)定的結(jié)構(gòu),SEM表明這些配位聚合物具有球狀的形貌,BET比表面積在40.3-95.4m2·g-1之間。多相催化實驗表明,Fe-Pp3、Co-Pp3、Cu-Pp3和Mn-Pp3對芳香烷烴具有較高的的催化氧化活性,催化劑循環(huán)使用3次后仍可以保持較高的催化活性。
[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，

本文編號：2013305