Study On The Metal Complexes Of Ethoxycarbonyl Substituted Porphyrin And Corrole

Porphyrins,corroles and their metal complexes have been widely used such as chemical sensor,optical materials,supramolecular self-assembly and dye-sensitized solar cell.These tetrapyrrole macrocyclic metal complexes have been widely used in catalysis chemistry and chemical biology.Metalloporphyrins can catalyze a variety of organic reactions,the most attention on the catalytic oxidation of organic substrate.Although a variety of metalloporphyrins catalysts have already synthesized,it is not common for catalysts to be recycled in homogeneous systems.In addition,the application of metalloporphyrins in the cross-dehydrogenative coupling(CDC)reaction is rare;it is need to explore the importance of this issue.In terms of chemical biology,new porphyrins photosensitizer research is very important for the development of PDT.Planar porphyrins play an important role in DNA binding and photophysical properties.5,10,15,20-tetra(ethoxycarbonyl)porphyrin(TECP)is a kind of good electron-deficient planar porphyrin,and is also a very effective precursor for the preparation of porphine.Since the first synthesis of TECP,it could not obtain much attention due to the complexity of its synthetic method.The properties and application of its metal complexes need further study.In this thesis,we improved the synthesis of TECP and prepared a series of metal TECP complexes and then the structures of these compounds have characterized.2,3,7,8,12,13,17,18-Octafluoro-5,10,15,20-tetra(ethoxycarbonyl)porphyin(F8-TECP)and its Zn complex have been synthesized.We investigated the catalytic activity of MnTECP in the catalytic oxidation of styrene.We studied CuTECP catalyzed CDC esterification reaction between carboxylic acid and organic substrate.We investigated the PDT antitumor activity of TECP,ZnTECP,GaTECP and SnTECP.5,10,15-tris(ethoxylcarbonyl)corrole(TECC)and its P,Ga,Sn and Co complexes were synthesized and characterized.We studied the photophysical properties of TECC,PTECC,GaTECC and SnTECC.The thesis main contents as follows:(1)Synthesized TECP by the improved Lindsey method,which reduced the volume of the reactor and greatly improved the yield compared with the literature.MnTECP,FeTECP,CoTECP,NiTECP,CuTECP,ZnTECP,PdTECP,AgTECP,GaTECP and SnTECP were prepared.Characterized the crystal structures of TECP,MnTECP,FeTECP,NiTECP,CuTECP,ZnTECP,AgTECP and SnTECP.From their crystal structure,we can see that the porphyrins rings have good planarity compared with aryl-substituted porphyrins.Wherein MnTECP,CuTECP,ZnTECP,AgTECP and SnTECP showed six-coordinated central metal structure,and TECP and NiTECP showed the similar structure.The three-dimensional structure of these crystals consists of hydrogen bonds or ?...? stacking interactions.(2)The reaction of MnTECP catalytic oxidation of styrene investigated by using two different types of oxygen sources,TBHP and PhIO.When TBHP used as oxidant the reaction proceed through free radical mechanism and the main product is benzaldehyde.When using PhIO as oxidant the reaction carried out through oxygen-atom transfer mechanism and the main product is styrene oxide.In addition,investigated the stability of MnTECP before and after the catalytic reaction by infrared spectroscopy.It found that the chemical structure did not change before and after the catalytic reaction,and it still had good catalytic ability after reaction 5 cycles.The catalytic activity and stability of MnTECP are better than that of common tetraphenylporphyrin manganese(MnTPP).(3)CuTECP catalyzed aromatic acid with C(sp~3)-H substrates by the CDC reaction was investigated.The results showed that the highest reaction yield was obtained after 4 h of CuTECP concentration of 0.5 mol%,2 times equivalent of oxidant and temperature of 120 ?.CuTECP can effectively catalyze the dehydrogenation coupling reaction between carboxylic acid and C(sp~3)-H bond,and the aromatic carboxylic acid can obtain better yield.In addition,it found that the steric hindrance effect reduced the yield of the product.The mechanism of the experiment shows that the reaction is a free radical process and the intermolecular competing kinetic isotope effect(KIE)experiment indicated that C(sp~3)-H bond cleavage is the ratedetermining step of this reaction.(4)The photophysical properties of TECP,ZnTECP,GaTECP and SnTECP were tested by UV-Vis absorption spectroscopy,fluorescence spectroscopy and fluorescence lifetime.The darkcytotoxicity and photocytoxicity of A549,Hela,Hep G2 and BEAS-2B tumor cells were measured by using these porphyrin compounds.GaTECP has a good PDT effect on A549 cells and ZnTECP has a good PDT effect on Hep G2 cells.Both of GaTECP and ZnTECP can enter the tumor cells produce reactive oxygen species,and reduce mitochondrial membrane potential,inducing tumor cells apoptosis.In addition,Hep G2 cell cycle arrest experiments show that ZnTECP could block in the G2/M period.(5)5,10,15-tris(ethoxylcarbonyl)corrole and its P,Ga,Sn,Co complexes were synthesized and characterized.Crystal structure of CoTECC obtained and analyzed.The TECC,PTECC,GaTECC and SnTECC characterized by using UV-vis absorption spectra,fluorescence spectra,fluorescence lifetime,singlet oxygen generation and cyclic voltammetry properties.PTECC and GaTECC have strong fluorescence emission intensity,the order of fluorescence quantum yield is PTECC > GaTECC > TECC > SnTECC.The order of singlet oxygen yield is TECC > SnTECC > GaTECC > PTECC.Electrochemical results indicate a significant increase in the redox stability of the corroles by coordination to metal or nonmetal elements.