The Design, Synthesis And Spectrum Property Testing Of Wide Spectral Response Porphyrins

Porphyrin compounds have wide application in materials chemistry, nonlinear optical materials,catalysis science and photodynamic therapy，owing to their good light, heat, chemical stability. Classicporphyrin molecules are existing intrinsic gap beween Soret (B band) and Q bands. Owing to thedevelopment of single-molecule panchromatic porphyrin remains a molecular engineering challenge,much effort has been functionalized on the porphyrin β-position and meso position. Based on this idea, wedesigned and synthesized a series of β-naphthyl fused porphyrins via [4+2] cycloaddition reaction ofβ-vinyl tetraarylporphyrins as a diene and arylalkynyl as a dienophile. And the UV absorption andfluorescence emission spectra of target products are investgated. The main contents include the followingthree parts.In the first part, the meso-tetraarylporphyrins were synthesized by the classical Adler conditions; thenthe transition metal copper(II) acetates were inserted into porphyrins;9kinds of β-formyl-meso-tetraarylporphyrins were obtained. The Wittig reaction conditions were improved through utilizingPotassium tert-butanolate instead of Sodium hydride, n-Butyllithium etc, providing9kinds of β-vinyl-meso-tetraarylporphyrins.In the second part, the macrocycles porphyrins were synthesized through the Diels-Alder Reaction ofβ-Vinyl-meso-tetraarylporphyrins and aryne precursors. The influence of reaction solvent, the ratio ofsolvent, fluorine source and base on the reaction were investigated, the optimal reaction conditions(CsF/Cs2CO3;CH3CN:Toluene=1:4;100oC) were obtained, giving11kinds of naphthoporphyrincompounds in yield of19-90%. The aromatization products and cycloaddition products were obtainedwhen electron-donating groups on the meso-phenyl groups of the compounds(4-CH3-,4-CH3O-,4-CH2(CH3)2-,4-CH2CH2(CH3)2-) while only the aromatization products were obtained whenelectron-withdrawing groups on the meso-phenyl groups of the compounds(4-CF3-,2-Cl-). The twoisomers were obtained when the dienophiles were symmetrical structure and the mixtures couldn’t beseparated by column chromatography.In the third part, the porphyrin compounds9a-9k were investigated by UV-vis absorptionspectroscopy and fluorescence. The UV-vis absorption spectra of the compounds9a-9g were red shifted nomatter the electron-withdrawing groups nor electron-donating groups on the meso-phenyl groups of thecompounds, and the Soret absorption bands were red shifted11-24nm, the Q absorption bands were redshifted9-41nm compared with the material6a. The UV-vis absorption spectra of the compounds9h-9kthat the electron-donating groups on the arynes were red shifted, and the Soret absorption bands were redshifted20-29nm, the Q absorption bands were red shifted16-34nm. The results of the fluorescenceemission spectra show that the maximum emission peak of compounds9a-9k were at698nm, and were redshifted about30nm compared with the material6a. The results can provide theoretical basis for future applications in emitting materials, photovoltaic materials and modification of the porphyrin structure.In summary, β-Vinyl-meso-tetraarylporphyrins were obtained by a simple and safe way that usingpotassium tert-butanolate instead of sodium hydride, n-Butyllithium etc. The desired compounds can beobtained in high yield through the Diels-Alder reaction of β-Vinyl-meso-tetraarylporphyrins and aryneprecursors. The results of UV absorption spectra and fluorescence emission spectra showed that theresponse scope of visible light was broaden by extending π electron conjugated systems, and can providesome basis for the future applications in emitting materials, photovoltaic materials and modification of theporphyrin structure.