Synthesis and characterization of rare earth metal complexes with novel Schiff base

Objectives. The work set out to synthesize Schiff base ligands containing a hydrazone moiety of (Z)-2-((E)-1-hydroxyethylidene)hydrazineylidene)-2-phenylacetic acid, as well as their praseodymium, samarium, europium, and gadolinium complexes, and to study their structure.

Methods. The structure of ligands was identified by infrared (IR), ultraviolet (UV), and nuclear magnetic resonance (NMR) spectroscopy. The structure of the complexes was confirmed by elemental analysis, IR and UV spectroscopy, and thermogravimetric analysis.

Results. The Schiff base ligands containing a hydrazone moiety of (Z)-2-((E)-1-hydroxyethylidene)hydrazineylidene)-2-phenylacetic acid, as well as their praseodymium, samarium, europium, and gadolinium complexes, were synthesized using the authors’ procedure.

Conclusions. NMR and IR spectroscopic data confirm that the Schiff base ligand is in the keto form. There are three absorption bands in the wavelength range of 205–306 nm in the UV spectrum of the ligand. A bathochromic shift is observed in the spectrum of all complexes. The molar ratio of ligand and metal in the complexes was 3 : 1.

1. Golcu A., Tumer M., Demirelli H., Wheatley R.A. Cd(II) and Cu(II) complexes of polydentate Schiff base ligands: synthesis, characterization, properties and biological activity. Inorg. Chim. Acta. 2005;358(6):1785–1797. https://doi.org/10.1016/j.ica.2004.11.026

2. Sinha D., Tiwari A.K., Singh S., Shukla G., Mishra P., Chandra H., Mishra A.K. Synthesis, characterization and biological activity of Schiff base analogues of indole-3-carboxaldehyde. Eur. J. Med. Chem. 2008;43(1): 160–165. https://doi.org/10.1016/j.ejmech.2007.03.022

3. Abbasova G.D., Pashajanov A.M., Ganbarova M.I., Gasanova S.M., Mammadova Z.A., Nasibova A.M. Synthesis and characterization of new metal complexes with tridentate hydrazone ligand. Azerbaijan Chemical Journal. 2023;4: 84–90. https://doi.org/10.32737/0005-2531-2023-4-84-90

4. Mohamed G.G. Synthesis, characterization and biological activity of bis(phenylimine) Schiff base ligands and their metal complexes. Spectrochim. Acta A. 2006;64(1):188–195. https://doi.org/10.1016/j.saa.2005.05.044

5. Tofazzal M., Tarafder H., Ali M.A., Saravanan N., Weng W.Y., Kumar S., Tsafe N.U., Crouse K.A. Coordination chemistry and biological activity of two tridentate ONS and NNS Schiff bases derived from S-benzyldithiocarbazate. Trans. Met. Chem. 2000;25:295–298. https://doi.org/10.1023/A:1007044910814

6. Chandra S., Jain D., Sharma A.K., Sharma P. Coordination Modes of a Schiff Base Pentadentate Derivative of 4-Aminoantipyrine with Cobalt(II), Nickel(II) and Copper(II) Metal Ions: Synthesis, Spectroscopic and Antimicrobial Studies. Molecules. 2009;14(1):174–190. https://doi.org/10.3390/molecules14010174

7. Karmakar M., Chattopadhyay S. A comprehensive overview of the orientation of tetradentate N2O2 donor Schiff base ligands in octahedral complexes of trivalent 3d metals. J. Molec. Struct. 2019;1186:155–186. https://doi.org/10.1016/j.molstruc.2019.02.091

8. Abu-Dief A.M., Mohamed I.M.A. A review on versatile applications of transition metal complexes incorporating Schiff bases. Beni-Suef Univ. J. Basic Appl. Sci. 2015;4(2):119–133. https://doi.org/10.1016/j.bjbas.2015.05.004

9. More M.S., Joshi P.G., Mishra Y.K., Khanna P.K. Metal complexes driven from Schiff bases and semicarbazones for biomedical and allied applications: a review. Mater. Today. Chem. 2019;14:100195. https://doi.org/10.1016/j.mtchem.2019.100195

10. Khalil M.M.H., Ismail E.H., Mohamed G.G., Zayed E.M., Badr A. Synthesis and characterization of a novel Schiff base metal complexes and their application in determination of iron in different types of natural water. Open J. Inorg. Chem. 2012;2(2):13–21. http://dx.doi.org/10.4236/ojic.2012.22003

11. Kajal A., Bala S., Kamboj S., Sharma N., Saini V. Schiff Bases: A Versatile Pharmacophore. J. Catalysts. 2013;2013:893512. https://doi.org/10.1155/2013/893512

12. Alsaygh A., Al-Humaidi J., Al-Najjar I. Synthesis of Some New Pyridine-2-yl-Benzylidene-Imines. Int. J. Org. Chem. 2014;4(2). http://doi.org/10.4236/ijoc.2014.42013

13. Utreja D., Vibha B.S.P., Singh S., Kaur M. Schiff Bases and their Metal Complexes as Anti-Cancer Agents: A Review. Current Bioactive Compounds. 2015;11(4):215–230. http://doi.org/10.2174/1573407212666151214221219

14. Chaudhary N.K. Synthesis and medicinal use of Metal complexes of Schiff Bases. Bibechana. 2013;9:75–80. https://doi.org/10.3126/bibechana.v9i0.7178

15. Sheikhshoaie I., Ebrahimipour S.Y., Sheikhshoaie M., Rudbari H.A., Khaleghi M., Bruno G. Combined experimental and theoretical studies on the X-ray crystal structure, FT-IR, 1HNMR, 13CNMR, UV–Vis spectra, NLO behavior andantimicrobial activity of 2-hydroxyacetophenone benzoylhydrazone. Spectrochim. Acta A. 2014;124:548–555. https://doi.org/10.1016/j.saa.2014.01.043

16. Krishnamoorthy P., Sathyadevi P., Butorac R.R.,.Cowley A.H, Bhuvanesh N.S., Dharmaraj N. Copper(I) and nickel(II) complexes with 1 : 1 vs. 1 : 2 coordination of ferrocenyl hydrazone ligands: Do the geometry and composition of complexes affect DNA binding/cleavage, protein binding, antioxidant and cytotoxic activities? Dalton Trans. 2012;41:4423–4436. https://doi.org/10.1039/C2DT11938B

17. Sharma M., Chauhan K., Srivastava R.K., Singh S.V., Srivastava K., Saxena J.K., Puri S.K., Chauhan P. Design and Synthesis of a New Class of 4-Aminoquinolinyl- and 9-Anilinoacridinyl Schiff Base Hydrazones as Potent Antimalarial Agents. Chem. Biol. Drug Des. 2014;84(2): 175–181. https://doi.org/10.1111/cbdd.12289

18. Vyas K.M., Jadeja R., Patel D., Devkar R., Gupta V.K. A new pyrazolone based ternary Cu(II) complex: Synthesis, characterization, crystal structure, DNA binding, protein binding and anti-cancer activity towards A549 human lung carcinoma cells with a minimum cytotoxicity to non-cancerous cells. Polyhedron. 2013;65:262–274. https://doi.org/10.1016/j.poly.2013.08.051

19. Kratz F., Beyer U., Roth T., Tarasova N., Collery P., Lechenault F., Cazabat A., Schumcher P., Unger C., Falken U. Transferrin Conjugates of Doxorubicin: Synthesis, Characterization, Cellular Uptake, and in Vitro Efficacy. J. Pharm. Sci. 1998;87(3): 338–346. https://doi.org/10.1021/js970246a

20. Jaividhya P., Dhivya R., Akbarsha M.A., Palaniandavar M. Efficient DNA cleavage mediated by mononuclear mixed ligand copper(II) phenolate complexes: The role of co-ligand planarity on DNA binding and cleavage and anticancer activity. J. Inorg. Biochem. 2012;114:94–105. https://doi.org/10.1016/j.jinorgbio.2012.04.018

21. Apelgot S., Coppey J., Fromentin A., Guille E., Poupon M., Roussel A. Altered distribution of copper (64Cu) in tumorbearing mice and rats. Anticancer Res. 1986;6(2):159–164. https://europepmc.org/article/med/3707051#impact

22. Hasinoff B.B., Yadav A.A., Patel D., Wu X. The cytotoxicity of the anticancer drug elesclomol is due to oxidative stress indirectly mediated through its complex with Cu(II). J. Inorg. Biochem. 2014;137:22–30. https://doi.org/10.1016/j.jinorgbio.2014.04.004

23. Ebrahimipour S.Y., Sheikhshoaie I., Crochet A., Khaleghi M., Fromm K.M. A new mixed-ligand copper(II) complex of (E)-N′-(2-hydroxybenzylidene) acetohydrazide: Synthesis, characterization, NLO behavior, DFT calculation and biological activities. J. Mol. Struct. 2014;1072:267–276. https://doi.org/10.1016/j.molstruc.2014.05.024

24. Marzano C., Pellei M., Tisato F., Santini C. Copper complexes as anticancer agents. Anticancer Agents Med. Chem. 2009;9(2): 185–211. https://doi.org/10.2174/187152009787313837

25. Garbutcheon-Singh K.B., Grant M.P., Harper B.W., Krause-Heuer A.M., Manohar M., Orkey N., AldrichWright J.R. Transition Metal Based Anticancer Drugs. Curr. Top. Med. Chem. 2011;11(5):521–542. https://doi.org/10.2174/156802611794785226

26. Vogel H.G. (Ed.). Drug Discovery and Evaluation: Pharmacological Assays. Berlin: Springer; 2008. 2068 p. http://dx.doi.org/10.1007/978-3-540-70995-4

27. Ebrahimipour S.Y., Sheikhshoaie I., Castro J., Haase W., Mohamadi M., Foro S., Sheikhshoaie M., Mahani S.E. A novel cationic copper(II) Schiff base complex: Synthesis, characterization, crystal structure, electrochemical evaluation, anti-cancer activity, and preparation of its metal oxide nanoparticles. Inorganica Chimica Acta. 2015;430:245–252. https://doi.org/10.1016/j.ica.2015.03.016

28. Sheikhshoaie I., Ebrahimipour S.Y., Sheikhshoaie M., Mohamadi M., Abbasnejad M., Rudbari H.A., Bruno G. Synthesis, characterization, X-ray crystal structure, electrochemical evaluation and anti-cancer studies of a mixed ligand Cu(II) complex of (E)-N′-((2-hydroxynaphthalen-1yl)methylene)acetohydrazide J. Chem. Sci. 2015;127(12): 2193–2200. https://doi.org/10.1007/s12039-015-0978-8

29. Guliyeva E.A., Fatullayeva P.A., Hagverdiyeva T.M. Synthesis and studies of Cu(II), Ni(II), Co(II) complexes with bis(saliciliden)hydrazon. Azerbaijan Chemical Journal. 2023;2:116–122. https://doi.org/10.32737/0005-2531-2023-2-116-122

30. Abbasova G., Medjidov A. One-pot Synthesis of a New Hydroxamic Acid and its Complexes with Metals. Letters in Organic Chemistry. 2022;19(10):837–841. http://doi.org/10.2174/1570178619666220111121743

31. Sarwar A., Shamsuddin M.B., Lingtang H. Synthesis, Characterization and Luminescence Studies of Metal-Diimine Complexes. Mod. Chem. Appl. 2018;6(3):1000262. http://doi.org/10.4172/2329-6798.1000262

32. Naemi H., Moradian M. Synthesis and characterization of nitro-Schiff bases derived from 5-nitro-salicylaldehyde and various diamines and their complexes of Co(II). J. Coord. Chem. 2010;63(1):156–162. http://doi.org/10.1080/00958970903225866

33. Nakamoto K. Infrared and Raman spectra of Inorganic and Coordination Compounds. Wiley; 1991. 410 p.

34. Calinescu M., Manea L., Pavelescu G. Synthesys and spectroscopic properties of new complex compounds of europium(III) and terbium(III) with 2-hydroxy-1naphthaldehyde acetylhydrazone and heterocyclic bases. Rev. Roum.Chim. 2011;56(3):231–237. http://web.icf.ro/rrch/

35. Tarasevich B.N. IK spektry osnovnykh klassov organicheskikh soedinenii (IR Spectra of the Main Classes of Organic Compounds). Moscow; MSU; 2012. 54 p. (in Russ.).