Synthesis And Spectral Properties Of C-annelated Pyrroles And Porphyrins With Exocyclic Rings

During the past few years, various porphyrins with exocyclic rings synthesized from c-annelated pyrroles were widely researched in the fields of photodynamic therapy, molcular wires, near-infrared dyes, fluorescent probes, molcular recognition, photosynthesis and so on. So a study on the synthesis of c-annelated pyrroles and porphyrins with exocyclic rings will undoubtedly help to develop novel porphyins with specific structures. The main contents of this thesis are as follows:1. The synthetic methodology of c-annelated pyrroles and porphyrins with exocyclic rings was briefly introduced and the development of the Barton-Zard reaction was sressed.2. Three kinds of representative c-annelated pyrrole, ethyl-cyclohexano[1,2,c] pyrrole-2- carboxylate,phenanthrolino[5,6,c] pyrrole-2- carboxylate and five new alkyl-8-tosyl- quinolino [5,6,c] pyrrole-2-carboxylates fused with aliphatic, aromatic and subsitituted rings respectively were synthesized and structurally characterized.3. An improvement, which adopt readily available inorganic base potassium carbonate instead of the organic base, 1,8-diazabicyclo[5.4.0] undec-7 -ene(DBU)and easily hydrolyzed tert-butoxide to the Barton-Zard reaction was employed during the synthesis of all the desired c-annelated pyrroles.The improved method was flexible and convenient to operate.4. The nonpolar meso-tetraphenyl-β-tetracyclohexanoporphyrin and its zinc complex were synthesized from ethyl-cyclohexano[1,2,c] pyrrole-2- carboxylate through Lindsey mothod. And another unsymmetrical porphyrins with exocyclic rings, phenanthrolinoporphyrin was synthesized from phenanthrolino[5,6,c] pyrrole-2- carboxylate through the"3+1"approach.5. The spectral properties of the fluorescent alkyl-8-tosyl- quinolino [5,6,c] pyrrole-2- carboxylates, meso-tetraphenyl-β-tetracyclohexanoporphyrin and its zinc complex and phenanthrolinoporphyrin were researched and the concentration quenching effect of the red light-emitting material expanded porphyrins and tetraphenylporphyrin was discussed.