Abstract: 3-Phen/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.

Key words: α-Oxygen-bearing substituted phthalocyanine, J-aggregate, Zn—O self-coordination