Synthesis Of Bisporphyrin-tripyrrin Metal Complexes And Investigation Of The Related Properties

In this dissertation, we have explored the syntheses of porphine and the relatedcompounds and have obtained5-formylporphines as the resulting compound.meso-Phenyl-substituted tripyrranes and tripyrrin-metal complexes were synthesized.The chelating properties of tripyrrins were characterized. Modified porphine ortetraphenylporphyrin structures were used to construct bisporphyrin structures linkedby tripyrrane or tripyrrin structures. The related stability information was revealed inthe reactions.The reaction conditions in the synthesis of porphine and its precursors have beenexplored. The Vilsmeier reactions and in-process demetalization of metalizedporphines have been investigated. It was found that copper(II)porphine was the properstarting material to synthesize5-formylporphyrin. The reaction was proved to be afacile route to synthesize5-formylporphyrin, which was also found to be unstableafter purification.The oxidation and chelation with metal atoms of meso-phenyl-substitutedtripyrranes have been explored. It was found that chloranil could oxidize tripyrraneinto symmetric tripyrrin, which was a reaction intermediate rather than the finaloxidation product. The range of metal atoms chelating with meso-phenyl-substitutedtripyrrins have been investigated. In comparison to the examples of metal atomschelating with meso-unsubstituted tripyrrins, meso-phenyl-substituted tripyrrins werefound to be a rigid structure. The fluorescence emission spectrum ofbis-(5,10-diphenyltripyrrin)nickel(II) was detected, showing that tripyrrin metalcomplexes have potential application potentials in the fields of fluorescent materials.Two methods to synthesize bisporphyrin structures linked by tripyrrane ortripyrrin have been attempted: condensation between formylporphyrin and pyrrole;Schiff base formation between formylporphirn and amino-modified tripyrranes ortripyrrins. Both attempts failed to achieve desired results. The steric hinderance of theporphyrin rings in the formylporphyrins were the obstacles in the condensationreactions; whereas the poor stability of tripyrrane or tripyrrin hindered the success ofthe Schiff base formation.