| Porphyrin compounds are cyclic structure which have 18π electron conjugated system, and are widely used in the aspects of photoelectricity, anti-cancer, analysis, catalysis and biosensing. In this thesis, 23 species of tetraphenylporphyrins, metal porphyrins and four kinds of Nconfused porphyrins, which were not reported in the literature, are designed and synthesized. The structures of the compounds are characterized by elemental analysis, IR and 1H NMR spectra. The crystal structures of 6 compounds are resolved by X-ray single crystal diffraction, and a series of novel structural metal porphyrin complexes are obtained. The UV-Vis absorption, fluorescence, electrochemical properties and the interaction with proteins and DNA of these compounds are studied.3,5-Dialkyl-4-hydroxybenzaldehydes are prepared by using the reaction of 2,6-dialkyl-4-hydroxyphenol with hexamine. According to Adler’s synthetic methods, 5,10,15,20-tetra(3,5-dimethyl-4-hydroxyphenyl)porphyrin(A1) and 5,10,15,20-tetra(3,5-diisopropyl-4-hydroxyphenyl)porphyrin(A11) are synthesized by the reaction of the aldehydes with equal molar pyrrole. The corresponding metalloporphyrin(A2-A7, A12-A17) are obtained by the reaction of A1 and A11 with transition metal acetates. A series of 4-alkoxybenzaldehydes are synthesized by the reaction of 3,5-dialkyl-4-hydroxybenzaldehyde and halohydrocarbon under alkaline conditions. Nine new porphyrin compounds are synthesized when reacted with pyrrole. They are 5,10,15,20-tetra(3,5-dimethyl-4-ethoxyphenyl) porphyrin(A8), 5,10,15,20-tetra(3,5-dimethyl-4-butoxyphenyl)porphyrin(A9),5,10,15,20-tetra(3,5-dimethyl-4-allyloxyphenyl)-porphy rin(A10), 5,10,15,20- tetra(3,5-diisopropyl-4-methoxyphenyl)porphyrin(A18), 5,10,15,20-tetra(3,5-diisopropyl-4-ethoxyphenyl) porphyrin(A19), 5,10,15,20-tetra(3,5-diisopropyl-4-butoxy-phenyl)porphyrin(A20),5,10,15,20-tetra(3,5-diisopropyl-4-allyloxyphenyl)porphyrin(A21),5,10,15,20-tetra(3,5-diisopropyl-4-benzyloxyphenyl)porphyrin(A22),5,10,15,20-tetra(3,5-diisopropyl-4-triphenyltinoxyphenyl)porphyrin(A23). These compounds are characterized by using IR, 1H NMR and X-ray single crystal diffraction. In A2, Zn atom possesses six-coordinated octahedral geometry, and the two-dimensional grid structure is formed through the coordination of intermolecular hydroxyl oxygen to zinc atom. Cu atom of A3 is four- coordinated planar quadrilateral, and a trwo-dimensional cellular supramolecular structure is formed by the intermolecular cyclic O-H···O hydrogen bonds. The molecular shape of A4 present the saddle type, and Ni is four-coordinated, and the molecules through intermolecular O-H···O hydrogen bonds are connected into three-dimensional supramolecular compound. Zn of A12 atom is four-coordinated, the molecules are joined into a two-dimensional network supramolecular structure through O-H···O hydrogen bond and Zn···O interaction(2.664 ?). The UV and fluorescence spectrum of the compounds indicate that the Soret band of the metalloporphyrins shows a red shift and the Q band shows a blue shift compared with free porphyrins.However, when hydroxyl is becomed into ether, the Soret and Q bands show a red shift. A11 and A14 are combined with protein in 1:1, and they also can insert into DNA base pairs to form a complex.According to Geier’s synthetic methods, the reactions of methyl p-formylbenzoate with pyrrole afford 4 kinds of N-confused porphyrin compounds which are characterized and studied by the same method as above. The UV absorption shows that there are a strong Soret band at about 441 nm and four absorption peaks of Q band at 500-750 nm. It turned out that the differences of the substituent have little influence on the UV of N-confused porphyrins.In this thesis, a variety of novel structural substituted phenylporphyrins and their metal complexs are synthesized, and their structures and properties are measured and studied.This work has enriched the content of the porphyrin chemistry and structural chemistry, and also laid a good foundation for the further research of other properties and applications of these compounds.
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