Synthesis, characterization and computational investigation of novel metalloporphyrazines containing 15-membered O2S2-donor macrocyclic moieties

Baygu Y., YILDIZ B., Karac I., DAL H., GÖK Y.

JOURNAL OF PORPHYRINS AND PHTHALOCYANINES, vol.22, no.1-3, pp.207-220, 2018 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 22 Issue: 1-3
  • Publication Date: 2018
  • Doi Number: 10.1142/s1088424618500104
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.207-220
  • Keywords: mixed-donor macrocycle, porphyrazine, template reaction, green chemistry, X-ray investigation, computational chemistry, SOLVENT-FREE CONDITION, MOLECULAR-STRUCTURE, STAR-PORPHYRAZINES, CRYSTAL-STRUCTURE, EFFICIENT METHOD, WET SIO2, COMPLEXES, ALCOHOLS, ENERGY, PHTHALOCYANINES
  • Anadolu University Affiliated: Yes


New metalloporphyrazines (MgPz, ZnPz) containing peripheral tetrasubstitutions derived from 7,8-dihydro-6H, 14H, 19H-dibenzo[bj][1,12,5,8]-dioxadithiacyclopentadecine-16,17-dicarbonitrile (6) have been synthesized by a multistep reaction sequence and characterized. Compound 6 has been prepared by the reaction of 1,3-di(2-bromomethyl phenoxy) propane (3) or 1,3-di(2-iodomethylphenoxy) propane (4) which were prepared via bromination or iodination of {2-[3-(2-hydroxymethylphenoxy) propoxy]-phenyl} methanol (2) and cis-1,2-dicyano-1,2-ethylenedithiolate (5). The novel magnesium porphyrazine was prepared by the cyclotetramerization reaction of 6 with magnesium butoxide. The one-step synthesis of porphyrazinato zinc complex has been achieved without a reaction sequence by using dicyano compound (6) and zinc butoxide. The prediction of the geometry optimization, normal mode frequencies, H-1, C-13 NMR, UV absorption spectra, chemical shifts, electronic properties and NBO analysis of the compound were examined by using B3LYP method with a 6-31G(d, p) basis set. These novel compounds were characterized by a combination of elemental analysis, H-1, C-13 NMR, FT-IR, UV-vis and MS spectral data. An X-ray crystal structure of dicarbodinitrile compound (6) was also investigated.