Synthesis and investigation of phenanthroline susbtitue ball-type phthalocyanines

Phthalociyanines are one of the macromolecules, which have increasing number of derivatives being synthesized and have greatly growing number of applications in various fields for decades. Phthalocyanines with different groups such as alkyl and aryl substituents on the periphery and non-periphery were synthesized in different types like mononuclear, polynuclear and ball-type and either with many metals in periodic table or metal-free. The Ball-type phthalocyanine was first synthesized by Tomilova et. al in 2002. Upto now, number of ball-type phthalocyanines containing different bridging groups such as aren, naphtalene, cumarine, pentaerithiole, rapidly increased and differrent properties, such as electrical, electrochemical, spectroelectrochemical, electrocatalytic, gas sensor, photophysical are studied. In the present work, 1,10-phenanthroline-4,7-disubstituted phthalonitrile 1 was prepared by the reaction of 4-hydroxophthalonitrile and 4,7-dichloro-1,10-phenanthroline in the presence of K2CO3. 4,7- phenanthroline substituted ball-type metal-free phthalocyanine 2 was obtained by the tetramerization of compound 1 in hydroquinone or tetramerization of compound with metalic lithium or MgCl2.6H2O and then its acidic hydrolysis. Metalloball-type phthalocyanines 3 and 4 were obtained by the reaction of compound 1 with Fe(AcO)2 or Mn(AcO)2.4H2O. 1,10-phenanthroline-5,6-disubstituted phthalonitrile derivative 6 was prepared by the reaction of 4-nitrophthalonitrile and 5,6-bis(2-hydroxoetoxy)-1,10-phenanthroline in the presence of K2CO3. 5,6-phenanthroline substituted ball-type metal-free phthalocyanine 7 was obtained by the tetramerization of compound 6 in hydroquinone or tetramerization of compound 1 with metalic lithium or MgCl2.6H2O and then its acidic hydrolysis. Metalloball-type phthalocyanines 8 and 9 were obtained by the reaction of compound 7 with Fe(AcO)2 or Mn(AcO)2.4H2O. Prepared compounds were characterized by 1H-NMR, 13C-NMR, UV-VIS, IR, mass spectrometers and elemental analysis. The aggregation behaviors of phenanthroline substituted phthalocyanines were studied depend on solvents and concentrations.