Axially-ligated Metalloporphyrins:Synthesis And Characterization

In our work,we introduced the substituents such as aryl-or azobenzol-group to the center meal of porphyrins by covalent bonding instead of coordinate bonding,while this process is carried out through cleavage of Ar-Br bond.Here are the results of our research:1.A series of Ⅷ metal tetra-(p-tolyl)-porphyrin complexes with axial phenyl substituents(1a-1b,2a-2c,3a-3c)have been synthesized and characterized.An aryl bromide cleavage reaction of transition metal complexes was used to prepare the complexes from Co(ttp),Rh(ttp)C1 and Ir(ttp)COC1,respectively.Magnetic circular dichroism(MCD)spectroscopy and TD-DFT calculations have been used to study trends in the optical spectra and electronic structures.The effect of introducing different para-substituents on the phenyl substituents was examined.During fluorescence emission studies,phosphorescence was observed for the Ir(Ⅲ)complexes in the near infrared(NIR)region.2.We synthesized Ir porphyrins with axial azophenyl and investigated its photochemical behavior.An aryl bromide cleavage reaction of transition metal complexes was used to introduce the azophenyl substituent through covalent binding.