Synthesis, Characterization And Properties Of Substituted Benzoporphyrin Tin And N-dislocated Porphyrin Benzoporphyrin

Porphyrins and metalloporphyrins have been one of the hotspots in organic synthesis.The tin atom of the metal tin porphyrin can combine with the electrophilic groups through oxygen atoms on the tin to form various types of axially coordinated porphyrin compounds,which are widely used in the aspects of photoelectricity,anti-cancer,analysis,catalysis and biosensing.In this thesis,21 substituted phenylporphyrin tins and 10 N-confused phenylporphyrins have been synthetized and characterized by means of IR,¹H NMR,elemental analysis and single crystal X-ray diffraction.Their structural self-assembly,UV-Vis absorption,fluorescence spectrum,and electrochemical properties.The phenylporphyrintin chlorides were prepared by using the reaction of the synthesised5,10,15,20-tetra?4-chlorophenyl?porphyrin?A₁?,5,10,15,20-tetra?4-methoxy-phenyl?porphyrin(A₁₁),and 5,10,15,20-tetra?4-butylphenyl?porphyrin(A₂₁)with stannous chloride.After the hydrolysis,the porphyrintin hydroxides were obtained.21 new trans-bis?carboxylato?-?5,10,15,20-tetraphenylporphyrinato?tin compounds were synthesized by the reaction of the different carboxylic acids,such as salicylic acid,trifluoroacetic acid,methylsulfonic acid,with the porphyrintin hydroxides,respectively.They are trans-bis?methylsulfonato??5,10,15,20-tetra?4-chlorophenyl?porphyrinato?tin?IV??A₄?,trans-bis-?methoxyacetnato?-?5,10,15,20-tetra?4-c hlorophenyl?porphyrinato?tin?A₅?,trans-bis?trifluoroacetonato??5,10,15,20-tetra?4-chlorophen-yl?porphyrinato?tin?A₆?,etc..Their structures were characterized by elemental analysis,IR,¹H NMR and single crystal X-ray diffraction.The crystal structures of 9 porphyrintin compounds were analyzed,and the intermolecular interactions in the crystal were discussed.One dimensional chain and two dimensional net supramolecular structures were formed by the intermolecular C-H…O and C-H…?weak interactions.The UV spectra indicate that the Soret bands of the porphyrintin compounds appear a red shift compared with the cooresponding porphyrin compounds,and the Soret band occur the blue shift when the chlorine atoms are replaced by the oxygen-contained groups.The fluorescence spectra show that the excitation wavelength of the porphyrintin compound is at 430 nm,and the maximum emission wavelength is blue shift compared with that of porphyrin compounds.The electrochemical property tests show that ferrocenecarboxylic acid phenylporphyrintins have three oxidation peaks and the other porphyrintin compounds have only one oxidation peak.In dichloromethane,2 N-confused porphyrin compounds,5,10,15,20-tetra?4-fluorophenyl?-N-confused porphyrin?B₁?and 5,10,15,20-tetra?4-phenyl?-N-confused porphyrin?B₉?,were obtained by the condensation of benzaldehyde or 4-fluorobenzaldehyde with pyrrole under the catalysis of methylsulfonic acid and DDQ oxidation.By alkylation reaction,8 new N-substituted N-confusedporphyrins,2-N-ethyloxycarbonylmethyl-5,10,15,20-tetra?4-fluorophenyl?-N-confused porphyrin?B₂?,2-N-carboxylmethyl-5,10,15,20-tetra?4-fluorophenyl?-N-confused porphyrin?B₃?,2-N-cycloamyloxycarbonylmethyl-5,10,15,20-tetra?4-fluorophenyl?-N-confused porphyrin?B₄?.Their structures were confirmed by elemental analysis,IR,¹H NMR and X-ray single crystal diffraction.The crystal structures of two N-confused porphyrin compounds were resolved.The results of the spectral analysis show that the excitation wavelengths of N-confused porphyrin are at 420 nm,and the maximum emission wavelengths are red-shifted when the N-confused porphyrin coordinated to metal ions.The synthesis,structure and properties of porphyrintins and N-confused porphyrins in this thesis were explored.This work not only expands the content of porphyrin chemistry,but also enrichs the structural data of porphyrin compounds,and provides the experimental basis for further studying their properties and applications.