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

Abstract

New metalloporphyrazines (MgPz, ZnPz) containing peripheral tetrasubstitutions derived from 7,8dihydro6H,14H,19Hdibenzo[bj] [1,12,5,8]dioxadithiacyclopentadecine16,17dicarbonitrile (6) have been synthesized by a multistep reaction sequence and characterized. Compound 6 has been prepared by the reaction of 1,3di(2bromomethyl phenoxy) propane (3) or 1,3di(2iodomethylphenoxy) propane (4) which were prepared via bromination or iodination of {2[3(2hydroxymethylphenoxy) propoxy]phenyl} methanol (2) and cis1,2dicyano1,2ethylenedithiolate (5). The novel magnesium porphyrazine was prepared by the cyclotetramerization reaction of 6 with magnesium butoxide. The onestep 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, 1 H, 13 C NMR, UV absorption spectra, chemical shifts, electronic properties and NBO analysis of the compound were examined by using B3LYP method with a 631G(d, p) basis set. These novel compounds were characterized by a combination of elemental analysis, 1 H, 13 C NMR, FTIR, UVvis and MS spectral data. An Xray crystal structure of dicarbodinitrile compound (6) was also investigated.

Novel nonperipheral octa-3-hydroxypropylthio substituted metallo-phthalocyanines: synthesis, characterization, and investigation of their electrochemical, photochemical and computational properties

“…The Φ d value of zinc(II) phthalocyanine was found in the order of 3.79 × 10 -5 in DMSO. This value is slightly higher than unsubstituted zinc(II) phthalocyanine [37,43].…”