New olefinic centred binuclear clamshell type phthalocyanines: Design, synthesis, structural characterisation, the stability and the change in the electron cloud at olefine-based symmetrical diphthalonitrile fragment by the combined application of UV-Vis electronic structure and theoretical methods

DEĞİRMENCİOĞLU İ., Bayrak R., Er M., SERBEST K.

POLYHEDRON, vol.30, no.9, pp.1628-1636, 2011 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 30 Issue: 9
  • Publication Date: 2011
  • Doi Number: 10.1016/j.poly.2011.03.039
  • Journal Name: POLYHEDRON
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.1628-1636
  • Karadeniz Technical University Affiliated: Yes

Abstract

The olefinic centred Schiff base (3) was obtained from the condensation of substituted dialdehyde (1) with 2-amino-4-methylphenol (2) in a 1:2 ratio. The diphthalonitrile derivative (5) was prepared by the reaction of 4-nitrophthalonitrile (4) and compound (3) in dry dimethylformamide/potassium carbonate. The key product (5) was obtained by nucleophilic substitution of an activated nitro group into an aromatic ring. The cyclotetramerization of compound (5) with phthalonitrile (6) in 1:6.15 ratio gave the expected metal-free phthalocyanine of clamshell type (7), and with metal salts of Zn(II), Ni(II), Co(II) and Cu(II) gave metallophthalocyanines of clamshell types (8-11), respectively in dimethylaminoethano1/1,8-diazabycyclo[5.4.0]undec-7-ene system. The products were purified by several techniques such as crystallization and preparative thin layer chromatography. The newly prepared compounds were characterised by a combination of elemental analyses, IR, (1)H/(13)C NMR, MS and UV-Vis spectroscopy. (C) 2011 Elsevier Ltd. All rights reserved.