Synthesis And Functional Studies On Carbazole Metalloporphyrin Complexes

Porphyrin and its derivatives are a class of highly conjugated system of aromatic compounds, H on the pyrrole ring N is very lively, it will generate the corresponding metalloporphyrin complex after the H is replaced by the metal autom. The metal porphyrin complexes have applications widely in bionics, solar energy, medicine, chemistry, special materials, catalysis and so on. Therefore, the scientists are interested in the studies of metalloporphyrin complexes, and have various experimental study to study about simulating the biological function, and do a lot of related work. At the same time, The special nature of their application are used in various technological fields, thus promoting the development of science.In this paper, we see carbazole as the starting materials, making full use of the lively H on the carbazole N to finish the replacement of alky, then synthesize aldehydes using Vilsmeier reaction, and then synthesize three different long-chain N-alky carbazole porphyrin ligand using the as-synthesized carbazole aldehyde and corresponding five transition metal porphyrin complexes and four lanthanide metal porphyrin complexes. They are characterized by means of UV-Vis, IR,1H NMR,MS and molar conductance. Furthermore, we have investigated thermal stability, electrochemistry property, redox property and liquid crystals property of these compounds by fluorescence spectroscopy, cyclic voltammetry, thermal analytical studies, XRD, DSC. The details are as follows:1:synthesis and characterization of N-alkyl carbazole porphyrin ligandsN-alkyl carbazole porphyrin ligand is synthesized through three steps, making carbazole as the starting material. Specific synthetic route as shown below: The products were characterized by UV-vis,1H NMR, MS, IR and molar conductance, which confirmed that it's the target product. Furthermore, we have investigated thermal stability, electrochemistry property, and fluorescence property of porphyrin ligands, and thermal analysis shows that the stability of the carbazole porphyrin is worse than usual porphyrin.2:synthesis and characterization of transition metal porphyrin complexesN-alkyl Carbazole porphyrin ligand as raw material, we synthesized Mn, Co, Ni, Cu, Zn five carbazole porphyrin complex using Alder synthesis methods, the process is as follows:The products were characterized by UV-vis, 1H NMR, MS, IR, molar conductance, DTA-TGA analysis, and fluorescence spectra. Molar conductivity shows that the five metal porphyrins, only Mn compounds are 1:1 electrolytes, that is Mn is trivalent. Fluorescence spectra shows that:among five metal porphyrin complexes, in addition to Zn, the other compounds happened fluorescence quenching. Electrochemical analysis gives the confirmation:comparison with porphyrin ligands, metal porphyrins with the lower first oxidation potential is not prone to oxidation, and it is deducted due to the higher first reduction potential, which proved metalloporphyrin has rich redox properties.3:synthesis and characterization of rare earth metal porphyrin complexesRare earth metal has unique electronic structure compared to transition metal, so rare earth porphyrins have broad application prospects in many areas. In this chapter N-alkyl Carbazole porphyrin ligand as raw material, we synthesized Dy, Ho, Er, Gd, four carbazole porphyrin complexs, the process is as follows:The products were characterized by UV-vis,1H NMR, MS, IR, molar conductance, DTA-TGA analysis, and fluorescence spectra. Molar conductivity shows that the four rare earth metal porphyrins are non-electrolytic. Fluorescence spectra showed that:fluorescence quantum yield and fluorescence intensity of metalloporphyrin are greatly reduced. Thermal analysis results show that:the stability of metal porphyrins is better than porphyrin ligands. Electrochemical analysis gives the confirmation: lanthanide metalloporphyrin has rich redox properties.4. liquid crystal properties of Carbazole porphyrin and its metal complexes liquid crystal properties of N-alkyl carbazole porphyrin ligands and their metal complexes were studied by DSC, XRD. Studies show that only transition metal complexs have the the original liquid crystal, but the rare earth no longer metal complexs have no liquid crystal property. And the four porphyrins are room temperature liquid crystal.but their structure can not be confirmed.