Metallophthalocyanines derived with phenyl sulfide by bridging triazole using click chemistry: Synthesis, Computational Study, Redox Chemistry and Catalytic Activity

• Published in: Journal of molecular structure Vol. 1236; p. 130225
• Main Authors: Karaca, Hüseyin, Delibaş, Nagihan Çaylak, Sağlam, Serap, Pişkin, Hasan, Sezer, Serdar, Hökelek, Tuncer, Teker, Murat
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15-07-2021
• Subjects: catalysis; click; computational; Phthalocyanine; redox; triazole; Phthalocyanine; catalysis; click; triazole; computational; redox
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/j.molstruc.2021.130225

Synthesis and characterization of new metallophthalocyanines (M = Zn, Co (II) and Ni (II)) carrying four new triazole units in peripheral positions was presented in this paper. First, 4-(prop-2-yn-1-yloxy)phthalonitrile, 3, was synthesized. Second, azidomethyl phenyl sulfide, 4, was added to this structure in order to obtain a triazole unit catalyzed by sodium ascorbate and CuSO4.5H2O in DMSO. Common spectroscopic methods such as FT-IR, 1H-NMR, 13C-NMR, HRMS and UV-Vis spectroscopy techniques was used for characterization of synthesized structures. The molecular structure of the phthalonitrile compound 5 was confirmed by single-crystal X-ray diffraction experiment. Morover, by using HF and B3LYP method and 6–31++g(d,p) basis set, 1H and 13C NMR chemical shifts, IR and UV–vis spectrums were theoretically calculated in gas phase for the optimized structure of 5. The obtained FTIR spectra and NMR spectra showed that the desired molecules were synthesized, and mass spectra confirmed these molecules. Electronic absorption spectra have shown that phthalocyanines are non-aggregable molecules. The cyclic voltammetry data of the phthalocyanines has shown that the Pc-6 has two reduction reactions and two oxidation reactions while the Pc-7 and Pc-8 have one reduction reaction and one oxidation reaction. Furthermore, the cobalt(II)phthalocyanine, Pc-7, was investigated as oxidation catalyst for the catalytic oxidation of 2-mercaptoethanol. Turnover number, initial reaction rate and the oxygen consumption values were found in the catalytic oxidation of 2-mercaptoethanol as 18.09, 0.12 µmol.s−1 and 6.88 µmol.min−1, respectively.