Novel metal-free and nickel(II) phthalocyanines bearing four tetraazatrioxa macrotricycles on peripheral positions were synthesized. Metal-free phthalocyanine was prepared by the reaction of 9,10-(2',3'-dicyano)-8,11,21-trioxa-1,5,14,18-tetraazatrioxa [12,9,2.2(5,18)]heptacosane (4) with dry 2-(N,N-dimethylamino)ethanol under reflux, The nickel(II) phthalocyanine was synthesized by the anhydrous NiCl2 and compound (4) in dry ethylene glycol under reflux. We also used compound (4) and metal-free phthalocyanine (5) in solvent extraction for some transition metal ions. The new symmetrical compounds were characterized by elemental analysis, H-1, C-13 NMR, IR, UV-vis and mass spectral data. (c) 2006 Elsevier Ltd. All rights reserved.