Synthesis, Characterization And Application Of Octaphyrin And BODIPY Derivatives

With the rapid development of porphyrin chemistry,a new breakthrough has been made in the modification of porphyrin structure,which greatly enriches the research content in the field of porphyrin.Among them,the modification of porphyrin marocycle has attracted extensive attention.In general,they can be divided into two categories:Expanded porphyrins and contracted porphyrins.In this thesis,I focused on the synthesis and study of novel octaphyrin and BODIPY complexes.Three novel octaphyrin complexes together with BODIPY derivatives have been synthesized.Their structures and properties are fully characterized.Moreover,these novel porphyrinoids can be used as probe for mercury???ion in solution and all of them shown high selectivity.First of all,we synthesized three novel octaphyrins.The structure of octaphyrins was determined by UV-vis spectra,nuclear magnetic resonance?NMR?spectra,high resolution mass spectra and crystal structure analysis.Compared with the traditional octaphyrins,the octaphyrins synthesized by us also adopt the“figure-of-eight conformation”.Till now the reported figure-of-eight structures,the central?,?-bipyrrole linkages have always adopted an anti-conformation.However,our complexes adopts a figure-of-eight conformation with syn-?,?-bithiophene linkages.In addition,the chemical shift of NH for the octaphyrin complexes locate in the low field of 15.0 ppm,indicating that the molecule was anti-aromatic.We further studied the properties of octaphyrins,and found that the addition of mercury ions would cause significant red shift in the UV-vis spectrum,which shift about 150 nm,but did not respond to other metal ions,shown that such complex have highly selectivity for mercury ions in the solution.To the second part,we introduce phenol-hydroxyl styrene group to the 3,5-position of BODIPY.The medication cause the absorption spectrum and fluorescence emission spectrum of the parent BODIPY shown large redshifted by nearly 100 nm respectively.Moreover,this type of BODIPY derivative is highly selective to mercury???ions in the solution.During the addition of mercury ioabsorption ns,the spectrum of the compound shown significant blue shift,while fluorescence spectrum was quenched at the same time.The detection limit of mercury ions obtained by the titration experiment of mercury???ions was 0.7?M.The binding constant of the fluorescent probe to mercury ions was 4.3×10³ M^-1.