The Design, Synthesis And Performance Testing Of Asymmetric5,15-substituted Porphyrins

By the p of porphyrin compounds with unique aromatic system structure,the compound and its metal complexes are often have strong spectral response and absorption of moderate intensity in400～450nm and450-550nm, thus they have excellent light, heat and chemical stability, since they are a kind of potential and environmental friendly photoelectric conversion material to be a hot topic in the study of people in the world. The literature shows that we can begin with the electronic structure of porphyrin, through adjusting and modifying to match the solar spectrum.In order to cause p-p*level splitting and lower HOMO-LUMO bandwidth,we can do by the following methods, firstly:expand the porphyrin p electronic conjugation; secondly:lower the symmetry of the porphyrin ring. Through these methods can we make the absorption of porphyrin redshift and wider, and relative to the Soret band, the absorption of Q band intensity will be improved significantly. In this case, due to improve the light absorption of porphyrin, the corresponding performance of the porphyrin dyes should be improved. In porphyrin β bit into the conjugated system and to realize the porphyrin p electronic conjugate system expands, so this thesis mainly carried out the following two aspects:1、the synthesis of2,2’-(phenylmethylene)bis(3,4-diphenyl-lH-pyrrole). Firstly iminodiacetic acid as a raw material to synthesis N-acetyl-imine base iminodiacetic acid dimethyl, on the basis of the condensation reaction with diaryl diketone,to synthesis3,4-diaryl pyrrole; By phosphoric acid catalyzed ring3,4-diaryl pyrrole with all sorts of replacing aromatic aldehyde condensation generating2,2’-(phenylmethylene)bis(3,4-diphenyl-lH-pyrrole).Find the suitable reaction conditions, catalysts, reaction material ratio and reach the ideal reaction yield. At the same time,considering the influence of aldehydes and the optimal reaction conditions,we get23compounds reported in literatures, and the structure of the compounds have been confirmed by1H NMR,13C NMR, melting point, mass spectrometry.2、The synthesis of asymmetric5,15-replace metal porphyrin and performance testing.We start with1,9-dimethyl acyl-meso aryl replace methylene pyrrole as raw material, under the condition of tetrahydrofuran as solvent, in situ generated at room temperature and normal propyl amine schiff base, decompression to tetrahydrofuran, add the anhydrous ethanol, anhydrous zinc acetate and synthesis of2,2’-(phenylmethylene)bis(3,4-diphenyl-lH-pyrrole) refluxed4-6hours, get a goal asymmetric5,15-substituted porphyrin compounds, the corresponding structure of porphyrin compounds by ultraviolet absorption spectra,1HNMR, and high resolution mass spectrometry to identify, through the confirmation of the structure of the porphyrin, we design the porphyrin reasonable structure, the design of the target compounds and spectroscopy performance to achieve the desired effect.