Synthesis and Biological Activity of Ni(II), La(III), and Ce(IV) Complexes with 8-Hydroxy-7-iodo-6-((4-sulfophenyl)diazinyl)quinoline-5-sulfonic Acid Ligand

https://doi.org/10.22146/ijc.110573

Noora Qasem Muhi(1*), Alyaa Khider Abbas(2)

(1) Department of Chemistry, College of Science, University of Baghdad, Al Jadriya Street, Baghdad 10071, Iraq
(2) Department of Chemistry, College of Science, University of Baghdad, Al Jadriya Street, Baghdad 10071, Iraq
(*) Corresponding Author

Abstract


In this study, a new azo ligand, 8-hydroxy-7-iodo-6-((4-sulfophenyl)diazinyl)quinoline-5-sulfonic acid (HAQ), was synthesized from 8-hydroxy-7-iodo-quinoline-5-sulfonic acid using a diazotization-coupling procedure and then complexed with La(III), Ni(II), and Ce(IV) ions. The ligand and its metal complexes were analyzed using elemental analysis, FTIR, UV-vis, 1H-NMR, TGA, SEM, ICP, and XRD techniques. Spectral and analytical results indicated the effective coordination of oxygen and nitrogen donor atoms, resulting in stable 1:1 (metal:ligand) of [La(HAQ)Cl2(H2O)2]·5H2O, and (1:2) of [Ce(HAQ)2(SO4)]·H2O and [Ni(HAQ)2(H2O)2]·4H2O complexes. Thermal analysis has revealed that metal complexes are more thermally stable than their corresponding free ligands. SEM showed significant morphological modifications during complexation, whereas XRD patterns revealed an increase in crystallinity in the metal complexes. The antioxidant characteristics of the synthesized compounds were evaluated using the phosphomolybdate technique, with the Ce(IV) complex displaying the highest activity, most likely due to its redox capacity. Overall, the results highlight the potential of HAQ and its metal complexes as promising candidates for antioxidant and anticancer applications. These findings warrant further mechanistic studies and in vivo evaluations.

Keywords


ferron-azo ligand; lanthanide; transition metal complexes; antioxidant activity; cytotoxicity



References

[1] Alghuwainem, Y.A.A., Abd El-Lateef, H.M., Khalaf, M.M., Abdelhamid, A.A., Alfarsi, A., Gouda, M., Abdelbaset, M., and Abdou, A., 2023, Synthesis, structural, DFT, antibacterial, antifungal, anti-inflammatory, and molecular docking analysis of new VO(II), Fe(III), Mn(II), Zn(II), and Ag(I) complexes based on 4-((2-hydroxy-1-naphthyl)azo) benzenesulfonamide, J. Mol. Liq., 369, 120936.

[2] Abd El-Lateef, H.M., Khalaf, M.M., Gouda, M., Amer, A.A., Abdelhamid, A.A., and Abdou, A., 2024, Design, synthesis of new mixed azo-hydroxyquinoline complexes; in vitro anti-inflammatory, antifungal, antibacterial, theoretical, and molecular docking interactions investigation, J. Mol. Struct., 1307, 138016.

[3] Rahman, M.M., Haque, T.M.A., Sourav, N.S., Rahman, S., Yesmin, S., Mia, R., Al Noman, A., and Begum, K., 2021, Synthesis and investigation of dyeing properties of 8-hydroxyquinoline-based azo dyes, J. Iran. Chem. Soc., 18 (4), 817–826.

[4] Abdel-Kader, N.S., Abdel-Latif, S.A., El-Ansary, A.L., and Hemeda, M.A., 2024, Design, synthesis, spectroscopic studies, DFT, TD-DFT/PCM calculations, and molecular docking studies on the anti-SARS and anti-COVID-19 activities of novel benzidine bis azo 1-(2-hydroxy-3-naphthoic acid) complexes with some transition metal ions, Polycyclic Aromat. Compd., 44 (6), 3601–3632.

[5] Martín-Montes, Á., Jimenez-Falcao, S., Gómez-Ruiz, S., Marín, C., and Mendez-Arriaga, J.M., 2023, First-row transition 7-oxo-5-phenyl-1,2,4-triazolo[1,5-a]pyrimidine metal complexes: antiparasitic activity and release studies, Pharmaceuticals, 16 (10), 1380.

[6] Joaquim, A.R., Pippi, B., de Cesare, M.A., Rocha, D.A., Boff, R.T., Staudt, K.J., Ruaro, T.C., Zimmer, A.R., de Araújo, B.V., Silveira, G.P., Martins, A.F., Teixeira, M.L., dos Santos, F.P., Fuentefria, A.M., and de Andrade, S.F., 2019, Rapid tools to gain insights into the interaction dynamics of new 8-hydroxyquinolines with few fungal lines, Chem. Biol. Drug Des., 93 (6), 1186–1196.

[7] Majidian, M., Raoof, J.B., Hosseini, S.R., Fischer, J., and Barek, J., 2020, Determination of 8-hydroxy-7-iodo-5-quinoline sulfonic acid (HIQSA) at renewable electrode with Sb2O3/MWCNT-TiO2 nanohybrid, J. Electroanal. Chem., 858, 113775.

[8] Soliman, A.Q.S., Abdel-Latif, S.A., Abdel-Khalik, S., Abbas, S.M., and Ahmed, O.M., 2024, Design, synthesis, structural characterization, molecular docking, antibacterial, anticancer activities, and density functional theory calculations of novel MnII, CoII, NiII, and CuII complexes based on pyrazolone-sulfadiazine azo-dye ligand, J. Mol. Struct., 1318, 139402.

[9] Eltaboni, F., Bader, N., El-Kailany, R., Elsharif, N., and Ahmida, A., 2022, Chemistry and applications of azo dyes: A comprehensive review, J. Chem. Rev., 4 (4), 313–330.

[10] Juvekar, V., Lim, C.S., Lee, D.J., Park, S.J., Song, G.O., Kang, H., and Kim, H.M., 2021, An azo dye for photodynamic therapy that is activated selectively by two-photon excitation, Chem. Sci., 12 (1), 427–434.

[11] Ghani, A.H., and Alabdali, A.J., 2022, Synthesis, characterization and anti-cancer activity of gold(III) and nickel(II) metal ion complexes derived from tetrazole–triazole compound, Al-Nahrain J. Sci., 25 (2), 8–13.

[12] Bao, G., Wen, S., Lin, G., Yuan, J., Lin, J., Wong, K.L., Bünzli, J.C.G., and Jin, D., 2021, Learning from lanthanide complexes: The development of dye-lanthanide nanoparticles and their biomedical applications, Coord. Chem. Rev., 429, 213642.

[13] Abo El‐Maali, N., Wahman, A.Y., Aly, A.A.M., Nassar, A.Y., and Sayed, D.M., 2020, Anticancer activity of lanthanum(III) and europium(III) 5‐fluorouracil complexes on Caco‐2 cell line, Appl. Organomet. Chem., 34 (6), e5594.

[14] Benkhaya, S., M'rabet, S., and El Harfi, A., 2020, Classifications, properties, recent synthesis and applications of azo dyes, Heliyon, 6 (1), e03271.

[15] Umamaheswari, M., and Chatterjee, T.K., 2008, In vitro antioxidant activities of the fractions of Coccinia grandis L. leaf extract, Afr. J. Tradit., Complementary Altern. Med., 5 (1), 61–73.

[16] Prieto, P., Pineda, M., and Aguilar, M., 1999, Spectrophotometric quantitation of antioxidant capacity through the formation of a phosphomolybdenum complex: Specific application to the determination of vitamin E, Anal. Biochem., 269 (2), 337–341.

[17] Bhat, M., and Marar, T., 2015, Cytotoxic effect of purified L-asparaginase from Salinicoccus sp. M KJ997975, Int. J. Curr. Microbiol. Appl. Sci., 4 (4), 701–712.

[18] Al-Jumaily, E.F., Al-Shanon, A.F., and Al-Barzanchi, S.I., 2015, Antioxidant and reactive oxygen species induction using purified natural lignan dimmer isolated from Myristica fragrans seed, World J. Pharm Res., 4 (3), 314–324.

[19] Adeniyi, A.O., Boyro, D.E.A., Chindo, I.Y., and Mahmoud, A.A., 2023, Spectrophotometric and infra-red analyses of azo reactive dyes derived from 2-methyl-3-(2’-methylphenyl)-6-arylazo-4-oxoquinazoline, Sci. World J., 18 (2), 231–239.

[20] Abdel-karim, A.M., Shahen, S., and Gaber, G., 2021, 4-Aminobenzenesulfonic acid as effective corrosion inhibitor for carbon steel in hydrochloric acid, Egypt. J. Chem., 64 (2), 825–834.

[21] Din Kadhoum Alzamili, S., Shamran Mohammed, H., and Mothhar Muslim, T., 2025, Biological activity of azo quinoline dye and its palladium(II) complex, Bull. Chem. Soc. Ethiop., 39 (1), 91–100.

[22] Abbas, R.A., Jarad, A.J., Nafliu, I.M., and Nechifor, A.C., 2019, Synthesis, characterization and antibacterial activity from mixed ligand complexes of 8-hydroxyquinoline and tributylphosphine for some metal ions, Rev. Chim., 70 (1), 36–40.

[23] Li, F.H., Liu, S.H., Guo, R.L., and Hou, H.Y., 2023, Thermal stability and decomposition mechanism analysis of 1,1’-azobis (cyclohexanecarbonitrile) by STA, DSC, ARC and TG-FTIR, J. Loss Prev. Process Ind., 83, 105044.

[24] Diab, M.A., El-Sonbati, A.Z., Gomaa, E.A., El-Mogazy, M.A., Morgan, S.M., Abou-Dobara, M.I., Omar, N.F., El-Zahed, M., and Osman, M.A., 2022, Polymer complexes: LXXIX—synthesis, characterization, geometrical structures, biological activity and molecular docking studies of azo dye complexes, J. Iran. Chem. Soc., 19 (7), 3079–3102.

[25] Ahmed, A.A., Peter, J.O., and Ngaramu, F.A.B., 2021, Synthesis and characterization of mixed ligand metal(II) complexes with Schiff base and 8-hydroxyquinoline as ligands, J. Chem. Lett., 2 (1), 43–49.

[26] Manulla, M.H., and Abbas, A.K., 2025, La(III) and Ce(IV) complexes of novel azo-theophylline ligand: Structural analysis and biological effectiveness, Iraqi J. Sci., 66 (1), 39–51.

[27] Hassan, A., Hemida, E., Mahmoud, N.I., Kamel, M., Elsharkawy, H.M., Khalil, A.S.G., Abdel-Hafiez, M., and Saber, M.R., 2025, Synthesis, structural characterization, and magnetic properties of two new Fe(III)Mn(III) 1D bimetallic compounds, ACS Omega, 10 (8), 8271–8280.

[28] Mohammed Noori Khaleel, A., 2025, Synthesis of indole borate ligand with Ni(II) and Cu(II) complexes, Bull. Chem. Soc. Ethiop., 39 (4), 703–712.

[29] Manulla, M.H., and Abbas, A. K., 2025, Design and structural characterization of novel azo-theophylline as acid-base indicator, Ibn AL-Haitham J. Pure Appl. Sci., 38 (2), 266–277.

[30] Alzamili, S.D.K., Mohammed, H.S., and Muslim, T.M., 2025, Biological activity of azo quinoline dye and its palladium(II) complex, Bull. Chem. Soc. Ethiop., 39 (1), 91–100.

[31] Yildiz, E.A., Pepe, Y., Erdener, D., Karatay, A., Boyacioglu, B., Ünver, H., Yapar, G., Demir, N., Yıldız, M., and Elmali, A., 2023, Colorimetric chemical sensing properties of 3-amino-4-hydroxybenzenesulfonic acid-based Schiff bases containing electron donor–acceptor groups, Chem. Phys., 574, 112048.

[32] Taher, D., AlNaimat, S., Assaf, K.I., Helal, W., and Korb, M., 2025, Synthesis of chloro‐substituted β‐ketiminate palladium complexes, spectral and thermal investigation of their structures, Eur. J. Inorg. Chem., 28 (6), e202400730.

[33] Radhi, E.R., Ali, F.J., and Ali, K.J., 2023, Synthesis and characterization of a new azo quinoline ligand and its metal complexes with spectrophotometric determination and biological efficacy study of its Hg(II) complex, Bull. Chem. Soc. Ethiop., 37 (6), 1423–1433.

[34] Al-mizher, T.T., and Abbas, A.K., 2025, Synthesis, identification, and biological evaluation of some metal ions complexes derived from thymine-azo ligand, Indones. J. Chem., 25 (3), 853–863

[35] Al-Saidi, H.M., Gouda, G.A., Abdel-Hakim, M., Alsenani, N.I., Alfarsi, A., Mahross, M.H., Farghaly, O.A., and Hosny, S., 2022, Synthesis and characterization of Ni(II), Cu(II), Zn(II) and azo dye based on 1,10-o-phenanthroline binary complexes: corrosion inhibition properties and computational studies, Int. J. Electrochem. Sci., 17 (3), 220333.

[36] Al-Zahraa, F., and Al-Hamdani, A.A.S., 2024, Synthesis, characterization, thermal studies, and antioxidant activities of azo dye[2-[(3-hydroxyphenyl)diazinyl]-1,2-benzothiazol-3(2H)-one-1,1-dioxide] and metal ion complexes, Iraqi J. Sci., 65 (12), 6842–6861.

[37] Mustapha, B., Saleh, A.A., El‐Seifat, R., Bufarwa, S., Hasan, H., and Moustafa, D., 2025, Exploring the antituberculosis, anti‐inflammatory, and antimicrobial activities and computational potential of quinoline‐8‐ol azo dye complexes, Appl. Organomet. Chem., 39 (8), e70310.

[38] Al-Adilee, K.J., and Hasan, S.R., 2021, Synthesis, characterization and biological activity of heterocyclic azo-Schiff base ligand derived from 2-amino-5-methyl thiazol and some transition metal ions, IOP Conf. Ser.: Earth Environ. Sci., 790 (1), 012031.

[39] Jedidi, I., Khemakhem, S., Saïdi, S., Larbot, A., Elloumi-Ammar, N., Fourati, A., Charfi, A., Ben Salah, A., and Ben Amar, R., 2011, Preparation of a new ceramic microfiltration membrane from mineral coal fly ash: Application to the treatment of the textile dying effluents, Powder Technol., 208 (2), 427–432.

[40] Mahmood, A.A., Hammadi, O.A., and Ibraheem, K.R., 2022, Preparation and photoluminescence spectra of organometallic complexes containing nanoparticles as random gain media, Indones. J. Chem., 22 (1), 205–211.

[41] Jahan Tamanna, N., Sahadat Hossain, M., Mohammed Bahadur, N., and Ahmed, S., 2024, Green synthesis of Ag2O & facile synthesis of ZnO and characterization using FTIR, bandgap energy & XRD (Scherrer equation, Williamson-Hall, size-train plot, Monshi-Scherrer model), Results Chem., 7, 101313.

[42] Abbas, N.F., and Abbas, A.K., 2020, Novel complexes of thiobarbituric acid–azo dye: Structural, spectroscopic, biological activity and dying, Biochem. Cell. Arch., 20 (1), 2419–2433.

[43] Fifere, N., Ardeleanu, R., Doroftei, F., Dobromir, M., and Airinei, A., 2024, Tailoring the structural and optical properties of cerium oxide nanoparticles prepared by an ecofriendly green route using plant extracts, Int. J. Mol. Sci., 25 (1), 681.

[44] Stepanov, S., 2021, New developments including X-ray standing waves in the dynamical Bragg diffraction program of X-ray server, J. Appl. Crystallogr., 54 (5), 1530–1534.

[45] Talal Ali Al-Rubaye, N., and Ali Salih Al-Hamdani, A., 2025, Synthesizing, characterization of some metal ion complexes with new azo dye and studying antioxidant and anticancer (MCF-7), Bull. Chem. Soc. Ethiop., 39 (5), 859–875.

[46] Banavar, S., Deshpande, A., Sur, S., and Andreescu, S., 2021, Ceria nanoparticle theranostics: Harnessing antioxidant properties in biomedicine and beyond, J. Phys.: Mater., 4 (4), 042003.

[47] Noriega, P., Gortaire, G., and Osorio, E., 2021, “Mass Spectrometry and Its Importance for the Analysis and Discovery of Active Molecules in Natural Products” in Natural Drugs from Plants, Eds. El-Shemy, H., IntechOpen, London, UK.



DOI: https://doi.org/10.22146/ijc.110573

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