Synthesis and EPR studies of porphyrazines with bulky substituents

KESKİN B., Koeseoglu Y., Avciata U., Guel A.

POLYHEDRON, vol.27, no.4, pp.1155-1160, 2008 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 27 Issue: 4
  • Publication Date: 2008
  • Doi Number: 10.1016/j.poly.2007.12.007
  • Journal Name: POLYHEDRON
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.1155-1160
  • Yıldız Technical University Affiliated: Yes


Magnesium porphyrazinate substituted with eight 4-tert-butylphenylthio-groups on the peripheral positions has been synthesized by cyclotetramerization of 1,2-bis(4-tert-butylphenylthio)maleonitrile in the presence of magnesium butanolate. The metal-free derivative was obtained by its treatment with trifluoroacetic acid and further reaction of this product with copper(II) acetate, zinc(II) acetate and cobalt(II) acetate led to the metal porphyrazinates (M = Cu, Zn, Co). These new compounds have been characterized by elemental analysis, together with FT-IR, (1)H NMR, UV-Vis spectral data. By using EPR technique, room temperature paramagnetic properties of Cu(II) doped porphyrazine sample as powder and solution forms were measured. The first-derivative EPR signals taken from as powder and solution forms shows that the sample is axially symmetric. The trend g(parallel to) > g(perpendicular to) > 2 indicates that the unpaired electron is located mainly in the d(x2-y2) orbital ((2)B(1) as ground state). (C) 2008 Elsevier Ltd. All rights reserved.