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

Abstract

The current study describes the synthesis, electrochemical, computational, and photochemical properties of octa (3-hydroxypropylthio) substituted cobalt (II) ( 4 ), copper (II) ( 5 ), nickel (II) ( 6 ) and zinc(II) ( 7 ) phthalocyanine derivatives. These novel compounds were characterized by elemental analysis, 1 H, 13 C NMR, FT-IR, UV-Vis, and MS. The redox behaviors of these metallo-phthalocyanines were investigated by the cyclic voltammetric method. The optimized molecular structure and gauge-including atomic orbital (GIAO) 1 H and 13 C NMR chemical shift values of these phthalocyanines in the ground state had been calculated by using B3LYP/6–31G(d,p) basis set. The outcomes of the optimized molecular structure were given and compared with the experimental NMR values. The photochemical properties including photodegradation and singlet oxygen generation of zinc(II) phthalocyanine were studied in DMSO solution for the determination of its photosensitizer behaviors.

Synthesis and Characterization of New-Type Soluble β-Substituted Zinc Phthalocyanine Derivative of Clofoctol

“…In the cathodic region, Zn(II)Pc 4 undergoes one well-defined one-electron process at −0.54 V and one split two-electron reduction at −1.37 V followed by two small backway oxidation waves at −1.49 V and at −1.04 V, respectively. In the anodic region, the oxidation waves at 0.43 V and 1.23 V are well seen and correspond to the data on Zn(II)Pc electrochemical behavior reported in the literature [17][18][19]. Thus, for instance, for octa-3hydroxypropylthio substituted Zn(II) phthalocyanine, the first oxidation wave was registered at 0.49 V, and the second one was observed at 0.98 V, and the processes have been assigned to the metal-and ring-based processes [1].…”

“…Zn(II)Pc 4 gives a ring-based redox process only due to the electro-inactive nature of the Zn(II) metal coordinated to the macrocycle, as the energy level of the d orbital of the zinc is placed out of the HOMO-LUMO energy levels [ 22 ]. This result may also be due to the smaller atomic radius of Zn(II) metal compared to other metal atomic radii such as Co and Mn [ 17 ].…”

“…Zn(II)Pc 4 gives a ring-based redox process only due to the electro-inactive nature of the Zn(II) metal coordinated to the macrocycle, as the energy level of the d orbital of the zinc is placed out of the HOMO-LUMO energy levels [22]. This result may also be due to the smaller atomic radius of Zn(II) metal compared to other metal atomic radii such as Co and Mn [17]. In the cathodic region, Zn(II)Pc 4 undergoes one well-defined one-electron process at −0.54 V and one split two-electron reduction at −1.37 V followed by two small backway oxidation waves at −1.49 V and at −1.04 V, respectively.…”