Synthesis, characterization and computational investigation of novel metalloporphyrazines containing 15-membered O2 S2-donor macrocyclic moieties

Abstract

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, 1H, 13C 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, 1H, 13C NMR, FT-IR, UV-vis and MS spectral data. An X-ray crystal structure of dicarbodinitrile compound (6) was also investigated. © 2018 World Scientific Publishing Company.