Octa‐substituted Zinc(II), Cu(II), and Co(II) phthalocyanines with 1‐(4‐hydroxyphenyl)propane‐1‐one: Synthesis, sensitive protonation behaviors, Ag(I) induced H‐type aggregation properties, antibacterial–antioxidant activity, and molecular docking studies

• Published in: Applied organometallic chemistry 2021-10, Vol.35 (10), p.n/a
• Main Authors: Bilgiçli, Ahmet T., Kandemir, Tugberk, Tüzün, Burak, Arıduru, Rana, Günsel, Armağan, Abak, Çağla, Yarasir, M. Nilüfer, Arabaci, Gulnur
• Format: Article
• Language: English
• Subjects: Agglomeration; antimicrobial and antioxidant; Antioxidants; Binding; Chelation; Chemistry; Copper; Ferrous ions; Fluorescence; H‐ or J‐type aggregation; In vitro methods and tests; Mathematical analysis; Metal ions; Metal phthalocyanines; Molecular docking; phthalocyanine; Protonation; Scavenging; Stoichiometry; Substitutes; Titration; Zinc
• ISSN: 0268-2605; 1099-0739
• DOI: 10.1002/aoc.6353

This study shows the synthesis and characterization of 4,5‐bis(4‐propionylphenoxy)phthalonitrile (2) and its octa‐substituted phthalocyanine derivatives [ZnPc(3), CuPc(4), and CoPc(5)]. A combination of standard spectroscopic techniques has characterized the newly synthesized phthalonitrile derivative and phthalocyanines. The aggregation behaviors of new octa‐substituted phthalocyanines have been evaluated by ultraviolet–visible (UV‐vis) spectroscopy. The metal ion‐sensitive behaviors of new octa‐substituted phthalocyanines in the presence of soft metal ions have been performed by UV‐vis and fluorescence spectrophotometer. The quenching efficiency (Ksv) of Ag+ ions against ZnPc(3) was found using the Stern–Volmer equation. The binding constant (Ka) and binding stoichiometry (n) of ZnPc(3) with Ag+ ions were calculated using the modified Benesi–Hildebrand equation. Sensitive protonation behaviors of octa‐substituted phthalocyanines have been investigated by titration experiments as well as computational calculations. The ZnPc(3) and CuPc(4) were exhibited H‐type aggregation behaviors toward Ag+ ions. However, the protonation of octa‐substituted zinc and copper phthalocyanine during the titration with HCl caused J‐type self‐aggregation properties. In vitro antioxidant properties of the new compounds were investigated by the radical scavenging ability of 1,1‐diphenyl‐2‐picrylhydrazyl (DPPH), chelating ability to ferrous ions, and reducing power methods. Additionally, in vitro antibacterial activities of the octa‐substituted phthalocyanines were determined. Finally, optimized structures of novel compounds [(2), ZnPc(3), CuPc(4), and CoPc(5)] were obtained on the HF (Hartree–Fock), B3LYP (Becke, 3‐parameter, Lee‐Yang‐Parr), M06–2X methods with 3–21 g, 6–31 g and SDD basis set. Then, biological activities of novel phthalonitrile and its phthalocyanine derivatives toward breast, liver, and lung cancer proteins were compared with molecular docking studies. The sensitive protonation and Ag+ ions behavior of octa‐substituted phthalocyanines were studied by UV‐vis and fluorescence spectroscopy, as well as computational calculations. In vitro antioxidant and antibacterial properties of the new octa‐substituted phthalocyanine derivatives were examined, and molecular docking studies evaluated the biological activities of novel compounds.