【作者】 洪湖铭；

【导师】 薛金萍；

【作者基本信息】 福州大学 ， 应用化学， 2005， 硕士

【摘要】 酞菁类配合物具有高度共轭的大环π电子体系,使酞菁类配合物显示出独特的光、电、热、磁的性质,有着广阔的应用前景。但由于其溶解性较差,限制了它的应用,人们通常通过对酞菁的分子结构进行必要的修饰,以改善其溶解性并获得所需的理化性质。本论文以此为出发点,合成了不同中心原子和在周环不同位置上带有不同类型氮杂芳氧基的新型酞菁金属配合物,并对它们进行了表征及相关性质研究。合成与表征: 1.本文合成了五种用于合成酞菁金属配合物的前驱体:3-(4-吡啶氧基)邻苯二甲腈、4-(4-吡啶氧基)邻苯二甲腈、4-(8-喹啉氧基)邻苯二甲腈、3-(2-甲基-8-喹啉氧基)邻苯二甲腈、4-(2-甲基-8-喹啉氧基)邻苯二甲腈。利用元素分析、IR 光谱、核磁共振氢谱、质谱等对其进行表征。2.合成了五个系列23 种的酞菁金属配合物:四-α-(4-吡啶氧基)取代酞菁金属配合物、四-β-(4-吡啶氧基)取代酞菁金属配合物、四-β-(8-喹啉氧基)取代酞菁金属配合物、四-α-(2-甲基-8-喹啉氧基)取代酞菁金属配合物、四-β-(2-甲基-8-喹啉氧基)取代酞菁金属配合物。利用元素分析、IR 光谱、UV/Vis 光谱、质谱对酞菁金属配合物进行表征。性质研究: 分别在不同溶剂中测定了所合成酞菁金属配合物的UV/Vis 光谱,结果表明:与无取代的金属酞菁配合物相比,本文所合成的取代酞菁金属配合物的Q带最大吸收波长都有较大红移;中心金属、溶剂、取代基种类对酞菁金属配合物的Q 带最大吸收波长影响较不明显;取代基的位置对Q 带最大吸收波长的影响较显著,α位取代的酞菁金属配合物比β位取代的Q 带最大吸收波长红移更为明显。同时,研究了四-β-(8-喹啉氧基)酞菁锌在DMF、DMSO 溶液中不同浓度时的聚集行为和四-β-(2-甲基-8-喹啉氧基)酞菁锌在DMF、DMSO 和THF 溶液中不同浓度时的聚集行为,发现这两种酞菁配合物在一定浓度范围内仍以单体形式存在。以DMF 为溶剂,测定了酞菁金属配合物的荧光光谱。从荧光光谱数据看,四-β-(8-喹啉氧基)酞菁镍,四-β-(8-喹啉氧基)酞菁锌,四-β更多还原

【Abstract】 Phthalocyanine compounds with large π-conjugated symstem in macrocycle display photo-electrical,thermal and magnetic peculiarity.They would be used widely in the future.Whereas,because they can’t be resolved easily,which limites their application. So the structure of phthalocyanine molecule has to be modified to improve their solubilities and obtain the required physical and chemical properties. Based on this,several metallophthalocyanines substituted with different types of azo-aromaticoxy in different position of the Pc ring were synthesized in this paper. These compounds were characterized and studied on properties. Synthesis and characterization: 1. Five precursors were synthesized in this paper which could be used to prepare metallophthalocyanines:3-(4-pyridyloxy)phthalonitrile,4-(4-pyridyloxy) phthalonitrile, 4-(8-quinolinoxy) phthalonitrile, 4-(2-methyl-8-quinolinoxy) phthalonitrile and 4-(2-methyl-8-quinolinoxy) phthalonitrile. And they were characterized by Elemental Analysis,IR,1HNMR as well as Mass spectrum. 2. Five series of substituted metallophthalocyanines (23 kinds) were synthesized: tetra -α-(4-pyridyloxy) metallophthalocyanines,tetra -β-(4-pyridyloxy) metallophthalocyanines, tetra-β-(8-quinolinoxy) metallophthalocyanines, tetra-α-(2-methyl-8-quinolinoxy) metallophthalocyanines and tetra -β-(2-methyl-8-quinolinoxy) metallophthalocyanines. They were characterized by Elemental Analysis, IR, UV-Vis as well as Mass spectrum. Study on properties: The UV/Vis spectrums of the metallophthalocyanines with different ring substituted groups were investigated in different solvent, As a result, in contrast to the corresponding non-substituted metallophthalocyanines, the λmax in Q-band of the metallophthalocyanines synthesized in thi paper shifted to red region observably.And The effects of central mental,solvent and the kinds of substituted groups on the metallophthalocyanines’λmax in Q-band were not distinct. The effects of substituted groups’position on the metallophthalocyanines’λmax in Q-band were much more distinct. For αsubstituted metallophthalocyanines,the λmax in Q-band shifted to red region more distinctly than that of βsubstituted metallophthalocyanines . The congregate behavior of tetra -β-(8 -quinolinoxy) phthalocyanine zinc( Ⅱ) with different concentrations in DMF and DMSO and tetra-β-(2-methyl -8-quinolinoxy) phthalocyanine zinc(Ⅱ) with different concentrations in DMF,DMSO and THF was discussed. The results indicated that the two kinds of metallophthalocyanines molecules are still monomer within certain concentration. Fluorescence spectrum of metallophthalocyanines was investigated in DMF,and the datas showed that the fluorescence decay life of tetra-β-(8-quinolinoxy) phthalocyanine nickel(Ⅱ), tetra-β-(8-quinolinoxy) phthalocyanine zinc(Ⅱ) as well as tetra-β-(4-pyridyloxy) phthalocyanine copper (Ⅱ) was 5.19ns,4.18ns and 4.58ns respectively.Furthermore,the three metallophthalocyanines had stonger fluorescence intensity than others and they would be used as fluorescence diagnosis agent in clinic. In N2 and O2 atmosphere,the metallophthalocyanines resolved in DMF were irradiated with different lamp-houses,and the photo-stable properties of the metallophthalocyanines were studied according to the varieties of UV/Vis spectrum.The results indicated that the effects of central mentals on the photostability of the metallophthalocyanines were distinctest,and the order of photo-stability was Zn<Ni<Cu<Co.更多还原