Synthesis Of Ester-substituded Phthalocyanines

Due to their unique structure and excellent performances in many fields, phthalocyanines have caused great interests of chemical workers since it was found. Numerous studies on phthalocyanines and their derivatives have been developed and found that phthalocyanine compounds had good thermal and chemical stability as well as the unique optical, electrical, magnetic, and catalytic performance. Therefore, phthalocyanines and their derivatives are widely used in many fields such as the pigment dye, chemical sensors, electric photochromic, liquid crystal material solar cells, and medical field. But theirs poor solubilities, difficulties in purification have greatly limits the application of phthalocyanines in the above fields. Modifying phthalocyanine rings’peripheral positions by ester groups can change electron density of the conjugated systems and also helps to decrease the aggregation between the phthalocyanine molecules to improve the solubility of the phthalocyanines. Anhydride-urea method is a common in carboxylic phthalocyanine complexes synthesis. However, the detailed characterizations of the esterification products have not yet been reported. And for the excellent performance of pure phthalocyanine isomers in organic semiconductors, nonlinear optical material etc., researches on preparation of the four constitutional isomers of phthalocyanine complexes have become one of the hot areas. So this thesis is divided into the following two parts:1. Preparation and characterization of octyloxy-carbonyl substituted phthalocyaninato metal complexesA series of octyloxy-carbonyl substituted phthalocyanine complexes with different metal atoms were synthesized by phthalic anhydride-urea methods using trimellitic anhydride and pyromellitic anhydride as starting materials separately. All these compounds were characterized by means of mass spectrometry, elemental analysis spectrometer,1H NMR spectrum for Zn[Pc(COOC8H17)4] providing additional unambiguous characterization for the identity of this compound. These complexes are soluble in chloroform, dichloromethane, toluene, xylene and other common organic solvents. We discussed their aggregation in different solvents (DMF, dichloromethane, chloroform, xylene, toluene, THF) under the concentration of5×10-6M. And the electronic absorption spectra and fluorescence emission spectra of compound Zn[Pc(COOC8H17)4] were recorded in concentration gradients. In addition, we identified the main functional groups from the spectra of infrared vibration and fully characterized by means of mass spectrometry, elemental analysis to these six compounds.2. Preparation, separation and characterization of pentyloxycarbonyl-phenoxy substituted phthalocyaninato metal isomersA series of α-tetrakis[(pentyloxycarbonyl)phenoxy]phthalocyaninato zinc(Ⅱ) complexes were synthesized using3-nitrophthalonitrile as the starting materials with DBU as the catalyst by cyclic tetramerization and transesterification. Simple silica-gel column chromatography leads to the successful separation of pure isomers with the C4h, and D2h symmetry together with a section containing the C2v and Cs isomers, which have been characterized with a wide range of spectroscopic methods including MALDI-TOF mass, electronic absorption,1H NMR, and2D COSY spectroscopy. We compared the chemical shift in1H NMR spectrum and the maximum absorption wavelength in electronic absorption spectra of constitutional isomers and discussed effect of steric hindrance of substitutents on the yield of various constitutional isomers.