Synthesis, characterization and electrochemical properties of novel metal free and zinc(II) phthalocyanines of ball and clamshell types

Ceyhan T., Altindal A., Ozkaya A. R., Celikbicak O., Salih B., Erbil M. K., ...More

POLYHEDRON, vol.26, no.15, pp.4239-4249, 2007 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 26 Issue: 15
  • Publication Date: 2007
  • Doi Number: 10.1016/j.poly.2007.05.028
  • Journal Name: POLYHEDRON
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.4239-4249
  • Istanbul Technical University Affiliated: No


The phthalodinitrile derivative I was prepared by the reaction of 4-nitrophthalonitrile and 1,3-dimethoxy-4-tert-butylcalix[4]arene in dry dimethylsulfoxide as the solvent, in the presence of the base K2CO3, by nucleophilic substitution of an activated nitro group in an aromatic ring. The tetramerization of compound I gave a binuclear zinc(II) phthalocyanine and a metal-free phthalocyanine of the ball type, 2 and 3, respectively. Its condensation with 4,5-bis(hexylthio)phthalonitrile results in a binuclear plithalocyanine of the clamshell type, 4. The newly synthesized compounds were characterized by elemental analysis, UV-Vis, IR, MS and H-1 NMR spectra. The electronic spectra exhibit an intense pi -> pi* transition with characteristic Q and B bands of the phthalocyanine core. The electrochemical properties of 2-4 were examined by cyclic voltammetry in non-aqueous media. The voltammetric results showed that while there is no considerable interaction between the two phthalocyanine rings in 4, the splitting of a molecular orbital occurs as a result of the strong interaction between the phthalocyanine rings in 2 and 3. (c) 2007 Elsevier Ltd. All rights reserved.