Novel Carboxyl Porphyrin And Porphyrin Coordination Compounds:Synthesis, Characterization And Their Catalysis Properties

Porphyrin which is aromatic macrocycle compound with 18 ? electrons shows special morphology and outstanding property. Porphyrin functional material has been promising potential application in gas adsorption, gas separation, catalyze, photo-electric transfer and non-linear optics. Especially in catalysis, porphyrin porous material surmount disadvantage of porphyrin molecule working as catalyst, which make them higher catalytic activity. For such reasons, porphyrin porous material has attracted much reach attention in recent years.Based on described research background, we designed novel porphyrin molecules, and used them to constructe porphyrin porous materials, and then we further exploited porous property and catalytic activity of porphyrin porous materials. The detail research content included:Firstly, eight metal-free porphyirns were successfully synthesized. They are: 5,10,15,20-tetra?4-?4-formateethyl?phenoxy?phenyl porphyrin ?H₂Pp1?,5,10,15,20-tetra?4-?4-carboxyl?phenoxy?-phenyl porphyrin ?H₂Pp2?,5,10-di?4-?4-formateethyl? phenoxy?phenyl-15,20-diphenyl porphyrin ?H₂Pp3?,5,10-di?4-?4-carboxyl? phenoxy?phenyl-15,20-diphenyl porphyrin ?H₂Pp4?,5,10-di?4-?4-formateethyl? phenoxy?phenyl-15,20-di?4-tertbutyl?phenylporphyrin ?H₂Pp5?,5,10-di?4-?4-carboxyl?phenoxy?phenyl-15,20-di?4-tertbutyl?phenylporphyrin ?H₂Pp6?,5,10-di ?4-?4-formateethyl?phenoxy?phenyl-15,20-di?4-pyridyl?phenyl porphyrin ?H₂Pp7?, 5,10-di?4-?4-carboxyl?phenoxy?phenyl-15,20-di?4-pyridyl?phenylporphyrin ?H₂Pp8?. They were characterized by elemental analyses, FI-IR,1H NMR, MS and UV-vis etc.Secondly, we prepared several metal porphyrin compounds based on synthesized porphyrin. Five of metal porphyrins were characterized though X-ray single crystal diffraction:[?ZnPp1??DMF?]·DMF ?1?, ?CuPp1?·?DMF? ?2?, ZnPp9 ?3?, ?CoPp2?·2DMF ?4? ?NiPp2?·2DMF ?5?.4 exhibits not only permanent porosity, but also, more importantly, high catalytic efficiency and selectivity for oxidation of ethylbenzene to acetophenone in quantitative 83% yield. In addition to five single crystals, twelve coordination polymers constructed by the reaction of porphyrin and transition metals ?Mn, Co, Cu? and three coordination polymers formed by porphyrin and rare earth metals ?Nd?. The coordination polymer were characterized by FT-IR, solid state UV-vis, powder X-ray diffraction ?P-XRD?, Thermal Gravity Analysis ?TGA? and elemental analyses ?EA?.Finally, we put our major research attention into studying the catalytic activity of five frameworks ?crystals 1-5? and twelve coordination polymers. After optimizing reaction conditions, we evaluate the catalytic activity of compounds and the results show that:?1? the metal ion inserting into macrocycle of porphyrin showed crucial influence on material catalytic activity, among three transition metals ?Mn, Co, Cu?, Mnporphyrins showed the highest activity. ?2? The catalytic activity of porphyirn coordination polymers is higher than that of metal porphyrin molecule, and porphyirn coordination polymers is reusable catalyst.