Syntheses And Studies Of Derivatives Of Mono-(o-aminophenyl) Substituted Porphyrin

Since Collman'group developed the prominent synthetic models, picket-fence porphyrin, o-aminophenyl substituted porphyrins have been used as a building block to develop various model compounds. In this thesis, we have designed and synthesized the novel derivatives as biomimetic ligands. It covers the following two parts:i) porphyrin with intramolecular hydrogen bonds. ii) biomimetic ligands of nitric oxide reductase.1) Hydrogen bonds are the most common interactions in biological system. Herein, we have designed and synthesized a Schiff base porphyrin and its corresponding reducing species as models to study hydrogen bonding in porphyrins. The corresponding complexes, [Zn(SATPP)(CH3OH)] and [Zn(HATPP)] (H2SATPP, dianion of 5-(2-salicylideneaminophenyl)-10,15,20-triphenylporphyrin; H2HATPP, dianion of 5-(2-hydroxybenzylaminophenyl)-10,15,20-triphenylporphyrin), have been characterized by X-ray crystallography,1H NMR, mass spectroscopy and UV-vis spectroscopy etc. The structure of [ZnSATPP(CH3OH)] shows that phenol oxygen is involved in double hydrogen bonds:one is within salicyleneaminophenyl group, the other is between the coordinated methanol and phenol oxygen.1H NMR spectra suggest the binding of methanol to zinc is an equilibrium process in solution. Equilibrium constant determined by UV-vis measurements suggests the intramolecular hydrogen bond stabilizes the structure and the binding affinity increases over 10 times than corresponding TPP species.2) Nitric oxide reductase (NOR) can catalyze the reduction of NO to N2O. The active site is comprised of non-porphyrin/porphyrin dinulcear iron complex. We have designed and synthesized two non-porphyrin/porphyrins as potential models for NOR, and characterized them.In conclusion, we have synthesized and studied porphyrin with hydrogen bonds and biomimetic ligands of nitric oxide reductase, and made a solid foundation for the coming study on their complexes as models.