α-含氧取代酞菁的聚集性质研究

Studies on Aggregation Behavior of α-Oxygen-bearing Substituted Phthalocyanines

以3-硝基邻苯二腈为原料分别与苯酚和甲醇反应合成3-苯氧基邻苯二腈和3-甲氧基邻苯二腈,这些α-取代的邻苯二腈以二甲氨基乙醇为溶剂,在有无醋酸锌条件下环合,分别形成α-四苯氧基锌酞菁、α-四苯氧基无金属酞菁、α-四甲氧基锌酞菁、α-四甲氧基无金属酞菁,对产物结构进行了表征.光谱分析结果表明,此类锌酞菁在氯仿等非配位溶剂中能自发形成J型聚集体,其Q带出现一个红移吸收带,经UV-Vis光谱、荧光光谱及MALDI-TOF质谱分析表明,该聚集体的形成机理为基于酞菁分子间的锌-氧自配位相互作用.

3-Pben/methoxyphthalonitrile was obtained via the reaction of 3-nitrophthalonitrile with phenol/ methanol under the catalysis of anhydrous potassium carbonate, α-Aryl/alkoxy substituted phthalocyanines were synthesized by treating the corresponding substituted phthalonitriles in refluxing dimethylaminoethanol with or without metal acetate and were fully characterized by UV-Vis, ^1H NMR, MS spectra and elemental analysis. It was found that α-oxygen-bearing substituted zinc phthalocyanines 1 and 3 can form J-type aggregates easily in non-coordinating solvents. The MALDI-TOF MS for the samples of 1 prepared from chloroform solutions gives the monomer and aggregate signals. The aggregates are broken up when a coordinating solvent is added to the solution. A possible mechanism on the formation of this self-assembly was proposed, which it was driven by the complementary coordination of the ether oxygen in the aryl/alk-oxy groups of one molecule to the core Zn of another molecule of phthalocyanine.