Synthesis And Optical Propertie Of Porphyrin Complexes

Porphyrins are a class of macrocyclic molecules with highly conjugated properties,which are widely found in nature and organisms.They have strong absorption in the range of UV-visible and have been widely used in the fields of light energy conversion,photocatalysis,photodynamic therapy,fluorescence detector and so on.Photocatalysis of porphyrins(including covalent polymers and coordination polymers)have been extensively reported.However,there are a few reports of asymmetric A3B porphyrins and their complexes about photocatalysis.(Ⅰ)A series of porphyrins with groups of dipicolinates on the periphery were synthesized,and the Ru(Ⅱ)-Zn porphyrins complex were obtained by coordinating the asymmetric A3B zinc porphyrin ligand with Ru(Ⅱ).The structure of porphyrins was determined by NMR,HR-MS,IR,and so on;the photophysical properties were studied by UV-vis absorption spectrophotometer and fluorescence emission spectrometer;the structure of porphyrins was optimized by DFT theoretical calculation.Finally,it was found that the Ru(Ⅱ)-Zn-porphyrin complex showed good photocatalytic activity for thiocyanation of ketones(the yield could be above 90%)and thiocyanation of indoles C-3(the yield could be above 80%)when the dosage of catalyst was only 0.1 mol%.(Ⅱ)The research of lanthanide metal ions were sensitized has been popular.In this paper,coordinating synthesized asymmetric A3B zinc porphyrin ligand with lanthanide metal ions Yb(Ⅲ)to get Yb(Ⅲ)-zinc porphyrin complexe.The complex was characterized by IR.And the physical properties was determined by fluorescent emission spectrometer.The study found that the complex has the same emission band as Yb(Ⅲ)in the range of 940-1100 nm,and the quantum yield in this range accounts for 35 percent of the total yield.It is preliminarily believed that near-infrared fluorescence emission of the complex achieved through the "antenna effect" between the zinc porphyrin ligand and the lanthanide metal Yb(Ⅲ).(Ⅲ)In this paper,a new type of Tb(Ⅲ)metal-organic framework material was successfully synthesized by the method of multi-layer diffusion at room temperature.The synthesis method solves the problem of energy consumption in other synthesis methods.The photophysical properties of the material were characterized by UV-vis absorption spectrophotometer and fluorescence emission spectrometer.It was found that under excitation at 325 nm,the solid material had emission peaks at 488,545,587 and 621 nm,which were attributed to transitions of 5D4→7F6 5D4→7F5,5D4→7F4 and 5D4→7F3,respectively.The material can emit strong green light and has a quantum yield of 36.98%in the solid state.These results indicate that Tb(Ⅲ)can beedsensitize by the organic ligands.