Synthesis and characterization of novel metal-free and metallophthalocyanines peripherally fused to four 24-membered tetraoxatetraaza macrocycles

New metal-free 5 and metallophthalocyanines 6-11 (M = Cu, Ni, Co, Pb, Zn) fused in peripheral positions with four 24-membered tetraoxatetraaza macrocycles were prepared by cyclotetramerization of 24,25-dicyano-4,10,13,17-tetra(toluene-p-sulfonyl)-1,2,3,4,5,6,7.8,9,10,11,12,13,14,15,16, 17,18,19,20,21,22-didicontine-hydrobenzo[y][3,9, 12,18]tetraaza[1,7, 16,22]tetraoxatetradicontine in the presence of the corresponding metal salt or a strong organic base. While the N-tosylated derivatives of the phthalocyanines are soluble in common organic solvents, the detosylated derivative of copper phthalocyaninate is soluble in water. The aggregation properties of the phthalocyanines were also investigated as a function of concentration, solvent and oxidative medium. The new compounds are characterized by a combination of elemental analysis and H-1 NMR, C-13 NMR, IR, UV-vis and MS specral data. Copyright (C) 2001 John Wiley & Sons, Ltd.