Yeni Zn-salofen tipi kompleksin sentezi, karakterizasyonu ve fotokatalitik bozunma aktivitesi

Öz

Bu çalışmada, yeni bir p-toluidin-imino-5-metoksisalisilaldehit (PTL) bileşiğinin ve PTL-Zn(II) kompleksinin sentezlenmesi ve PTL-Zn(II) kullanılarak metilen mavisinin fotokatalitik bozunma aktivitesinin araştırılması amaçlanmaktadır. p-Toluidin-imino-5-metoksisalisilaldehit, p-toluidin ve 5-metoksisalisilaldehitin kondenzasyon reaksiyonu yoluyla sentezlendi. Daha sonra bu ligandın çinko(II) asetat ile alkollü ortamda reaksiyonu sonucunda yeni bir çinko(II) metal kompleksi hazırlandı. Sentezlenen PTL ve PTL-Zn(II)'nin yapıları FTIR, UV-Vis, 1H NMR, SEM ve element analiz teknikleri kullanılarak karakterize edildi. Spektroskopik ve analitik bulgular, sentezlenen PTL-Zn(II) kompleksinin 1:2 metal-ligand oranına ve tetrahedral bir geometriye sahip olduğunu doğrulamaktadır. Ayrıca, PTL-Zn(II) kompleksinin fotokatalitik özellikleri metilen mavisi (MB) kullanılarak araştırıldı. Metilen mavisi boyasının bozunması UV-Vis spektroskopisi kullanılarak izlendi ve boyanın yaklaşık %80'i 210 dakika sonra bozundu. Bu bulgular, PTL-Zn(II) kompleksinin suda çözünebilen endüstriyel boyaların bozunma uygulamaları için umut vadeden bir malzeme olduğunu göstermektedir.

Anahtar Kelimeler

• 5-metokksisalisilaldehit
• Çinko(II) kompleksi
• Fotokatalitik aktivite
• Metilen mavisi boyası

Synthesis, characterization of new Zn-salophene type complex and photocatalytic degradation efficiency

Abstract

This study aims to synthesize a novel p-toluidine-imino-5-methoxysalicylaldehyde (PTL) compound and PTL-Zn(II) complex, and investigate the photocatalytic degradation activity of methylene blue utilizing PTL-Zn(II). p-Toluidine-imino-5-methoxysalicylaldehyde was synthesized via a condensation reaction of p-toluidine and 5-methoxysalicylaldehyde. A new zinc(II) metal complex was then prepared by reacting this ligand with zinc(II)acetate in an alcoholic medium. The structures of the synthesized PTL and PTL-Zn(II) were elucidated utilizing FTIR, UV-Vis, 1H NMR, SEM, and elemental analysis techniques. Analytical and spectroscopic findings confirm that the synthesized PTL-Zn(II) complex has a 1:2 metal-ligand ratio and a tetrahedral geometry. Furthermore, the photocatalytic features of the PTL-Zn(II) complex were investigated using methylene blue (MB). The degradation of methylene blue was monitored utilizing UV-Vis spectroscopy, and approximately 80% of the dye was degraded after 210 minutes. These findings indicate that the PTL-Zn(II) complex is a hopeful material for degradation applications of water-soluble industrial dyes.

Keywords

• 5-methoxysalicylaldehyde
• Zinc(II) complex
• Photocatalytic activity
• Methylene blue dye

Kaynakça

1. M. N. Uddin, S. S. Ahmed and S. R. Alam, Biomedical applications of Schiff base metal complexes. Journal of Coordination Chemistry, 73(23), 3109-3149, 2020. https://doi.org/10.1080/00958972.2020.1854745.
2.     P. Pfeiffer, E. Breith, E. Lübbe and T. Tsumaki, Tricyclische ortho kondensierte neben valenz inge. Justus Liebigs Annalen der Chemie, 503(1), 84-130, 1933. https://doi.org/10.1002 /jlac.19335030106.
3.     I. Elaaraj, O. Oulidi, A. Nakkabi, L. Nalbone, G. Sorrentino, F. Giarratana and M. Fahim, Synthesis, characterization, and evaluation of biological activities of M(II) metal complexes (M=Co, Zn and Cu) based on a bidentate Schiff base ligand 2-((4-nitrobenzylidene) amino) phenol. Journal of Molecular Structure, 1351(2), 144362, 2025. https://doi.org/ 10.1016/j.molstruc.2025.144362.
4.     H. Kargar, A. A. Ardakani, M. N. Tahir, M. Ashfaq, and K. S. Munawar, Synthesis, spectral characterization, crystal structure determination and antimicrobial activity of Ni(II), Cu(II) and Zn(II) complexes with the Schiff base ligand derived from 3, 5-dibromosalicylaldehyde. Journal of Molecular Structure, 1229, 129842, 2021. https://doi.org/ 10.1016/j.molstruc.2020.129842.
5.     V. Rangaswamy, S. Renuka and I. Venda, Synthesis, spectral characterization and antibacterial activity of transition metal (II) complexes of tetradentate Schiff base ligand. Materials Today: Proceedings, 51, 1810-1816, 2022. https://doi.org/10.1016/j.matpr.2021.10. 360
6.     U. P. S. Prabhakar, G. Periyasami, and P. Karthikeyan, Nanostructured metal oxides synthesized via simple thermal decomposition of Co(II), Ni(II), Cu(II), and Zn (II) Schiff base complexes: characterization and antimicrobial activity. Inorganic Chemistry Communications, 159, 111796, 2024. https://doi.org/ 10.1016/j.inoche.2023.111796.
7.     T. Chowdhury, S. Dasgupta, S. Khatua, K. Acharya and D. Das, Executing a series of zinc(II) complexes of homologous Schiff base ligands for a comparative analysis on hydrolytic, antioxidant, and antibacterial activities. ACS Applied Bio Materials, 3(7), 4348-4357, 2020. https://doi.org/10.1021/acsabm.0c00372.
8.     C. M. Sharaby, M. F. Amine and A. A. Hamed, Synthesis, structure characterization and biological activity of selected metal complexes of sulfonamide Schiff base as a primary ligand and some mixed ligand complexes with glycine as a secondary ligand. Journal of Molecular Structure, 1134, 208-216, 2017. https://doi.org/10.1016/j.molstruc.2016.12.070.

9.     P. Durairaj, T. Maruthavanan, S. Manjunathan, S. Subashini, S. L. Rokhum and G. Baskar, Microwave assisted synthesis, characterization and bioactivity evaluation of a cobalt (II) complex with a novel Schiff base ligand derived from phenylacetyl urea and salicylaldehyde. Journal of Molecular Structure, 1295, 136650, 2024. https://doi.org/10.1016/j.molstruc.2023. 136650.
10.   S. O. Bahaffi, A. A. A. Aziz and M. M. El-Naggar, Synthesis, spectral characterization, DNA binding ability and antibacterial screening of copper (II) complexes of symmetrical NOON tetradentate Schiff bases bearing different bridges. Journal of Molecular Structure, 1020, 188-196, 2012. https://doi.org/ 10.1016/j.molstruc.2012.04.017
11.   A. Singh, H. P. Gogoi and P. Barman, Synthesis of metal oxide nanoparticles by facile thermal decomposition of new Co(II), Ni(II), and Zn(II) Schiff base complexes-optical properties and photocatalytic degradation of methylene blue dye. Inorganica Chimica Acta, 546, 121292, 2023. https://doi.org/ 10.1016/j.ica.2022.121292.
12.   M. Karmakar and S. Chattopadhyay, Visible light driven photodegradation of methylene blue with two reduced Schiff base complexes of zinc (II): Exploration of their phosphatase mimicking ability. Polyhedron, 184, 114527, 2020. https://doi.org/ 10.1016/j.poly.2020.114527.
13.   S. R. Boruah, R. D. Purkayastha, L. Sieroń, W. Maniukiewicz, R. M. Gomila and A. Frontera, Trinuclear zinc (II)-Schiff base complex: synthesis, structural elucidation, DNA interactions and photocatalytic dye degradation. Journal of Molecular Structure, 1343, 142904, 2025. https://doi.org/10.1016/ j.molstruc.2025.142904.
14.   J. Ahemed, J. Pasha, R. Kore, R. Gade, Y. Bhongiri, P. Chetti and S. Pola, Synthesis of new Zn(II) complexes for photo decomposition of organic dye pollutants, industrial wastewater and photo-oxidation of methyl arenes under visible-light. Journal of Photochemistry and Photobiology A: Chemistry, 419, 113455, 2021. https://doi.org/10.1016/j.jphotochem.2021.113455.
15.   R. F. Li, C. Huang, Y. T. Hong, M. J. Tian, and B. X. Zhu, Zn(II) and Cu(II) complexes constructed from a Schiff base macrocycle: Synthesis, vapor adsorption and photocatalytic degradation properties. Journal of Molecular Structure, 1327, 141222, 2025. https://doi.org/10.1016/j.molstruc.2024.141222.
16.   S. Y. Uçan, Synthesis, spectral, thermal, and magnetic studies of cobalt(II), nickel(II), copper(II), zinc(II), and cadmium(II) complexes with N2O2 donor groups. Russian Journal of General Chemistry, 84(9), 1819-1824, 2014. https://doi.org/10.1134/ S1070363214090308.
17.   H. Barfeie, G. Grivani, V. Eigner, M. Dusek and A. D. Khalaji, Copper(II), nickel(II), zinc(II) and vanadium(IV) Schiff base complexes: Synthesis, characterization, crystal structure determination, and thermal studies. Polyhedron, 146, 19-25, 2018. https://doi.org/10.1016/j.poly.2018.02.012.
18.   S. Y. Uçan and B. Mercimek, Synthesis and characterization of tetradentate N2O2 Schiff base ligands and their transition metal complexes. Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, 35(3), 197-201, 2005. https://doi.org/ 10.1081/SIM-200037249.
19.   L. Q. Chai, J. Y. Zhang, L. C. Chen, Y. X. Li and L. J. Tang, Synthesis, crystal structure, spectroscopic properties and DFT calculations of a new Schiff base-type Zinc(II) complex. Research on Chemical Intermediates, 42(4), 3473-3488, 2016. https://doi.org/10.1007/s11164-015-2226-8.
20.   D. Dinku, T. B. Demissie, I. N. Beas, R. Eswaramoorthy, B. Abdi and T. Desalegn, Antimicrobial activities and docking studies of new Schiff base ligand and its Cu(II), Zn(II) and Ni(II) Complexes: Synthesis and Characterization. Inorganic Chemistry Communications, 160, 111903, 2024. https://doi.org/10.1016/j.inoche.2023.111903.
21.   S. Y. Uçan, Synthesis, morphology, spectral characterization and thermal behaviors of transition metal complexes containing oxime-imine group. Erzincan University Journal of Science and Technology, 13(3), 1263-1270, 2020. https://doi.org/ 10.18185/erzifbed.789893.
22.   E. S. Aazam, and R. Thomas, Synthesis, characterization, and electronic structure of bioactive vanillin based fluorescent Schiff bases. Journal of Molecular Liquids, 395, 123820, 2024. https://doi.org/ 10.1016/j.molliq.2023.123820.
23.   A. K. Dağ, New Schiff base ligands and their homoleptic Co(II)/Cu(II) complexes: synthesis, characterization and photocatalytic properties for degradation of methylene blue. Journal of Molecular Structure, 1327, 141185, 2025. https://doi.org/ 10.1016/j.molstruc.2024.141185.
24.   M. Muslim, A. Ali, M. Ahmad, A. Alarifi, M. Afzal, N. Sepay, and N. Dege, A zinc(II) metal–organic complex based on 2-(2-aminophenyl)-1H-benzimidazole ligand: exhibiting high adsorption capacity for aromatic hazardous dyes and catecholase mimicking activity. Journal of Molecular Liquids, 363, 119767, 2022. https://doi.org/10.1016/j.molliq.2022.119767
25.   S. Waseem, H. Saleem, M. N. Akhtar, M., Imran, A. Javaid, M. A. AlDamen, and M. A. Khanfar, A Zn-based Zig-Zag 1D chain type coordination polymer for removal of methylene blue dye from an aqueous solution. Inorganica Chimica Acta, 559, 121756, 2024. https://doi.org/10.1016/j.ica.2023.121756.
26.   E. U. Mughal, A. Javaid, M. Imran, M. A. Abourehab, E. B. Elkaeed, N. Naeem, and S. F. Kainat, Complexes of terpyridine scaffold as efficient photocatalysts for the degradation of methylene blue pollutant in wastewater effluents. Inorganica Chimica Acta, 546, 121329, 2023. https://doi.org/10.1039/d5ra01117e.
27.   J. Johnson, and A. Yardily, Co(II), Ni(II), Cu(II), and Zn(II) metal complexes of chalcone: Synthesis, characterization, thermal, antimicrobial, photocatalytic degradation of dye and molecular modeling studies. Applied Organometallic Chemistry, 36(1), e6465, 2022. https://doi.org/10.1002/aoc.6465.
28.   D. Dey, G. Kaur, M. Patra, A. R. Choudhury, N. Kole, and B. Biswas, A perfectly linear trinuclear zinc–Schiff base complex: Synthesis, luminescence property and photocatalytic activity of zinc oxide nanoparticle. Inorganica Chimica Acta, 421, 335-341, 2014. https://doi.org/10.1016/j.ica.2014.06.014.
29.   H. Wang, X. Y. Zhang, C. F. Bi, Y. H. Fan, and X. M. Meng, Synthesis, crystal structures and photocatalytic properties of Zn(II), Ni(II), Co(II) complexes with a symmetric open-chain N2O4-donor bis-Schiff base ligand. Transition Metal Chemistry, 40(7), 769-777, 2015. https.doi.org/10.1007/s11243-015-9975-5.
30.   P. Chung, Y. Huentupil, W. Rabanal, J. Cisterna, I, Brito, and R. Arancibia, Synthesis, characterization, X‐ray structure, electrochemistry, photocatalytic activity and DFT studies of heterotrinuclear Ni(II), Pd(II) and Zn(II) complexes containing a formyl ferrocene thiosemicarbazone ligand. Applied Organometallic Chemistry, 34(12), e5974, 2020. https://doi.org/ 10.1002/aoc.5974.
31.   A. Singh, H. P. Gogoi, and P. Barman, Synthesis of metal oxide nanoparticles by facile thermal decomposition of new Co(II), Ni(II), and Zn(II) Schiff base complexes-optical properties and photocatalytic degradation of methylene blue dye. Inorganica Chimica Acta, 546, 121292, 2023. https://doi.org/ 10.1016/j.ica.2022.121292.
32.   M. Karmakar, and S. Chattopadhyay, Visible light driven photodegradation of methylene blue with two reduced Schiff base complexes of zinc(II): Exploration of their phosphatase mimicking ability. Polyhedron, 184, 114527, 2020. https://doi.org/10.1016/ j.poly.2020.114527.
33.   M. Somnath, Ahmad and K. A. Siddiqui, A Zn-Polyrotaxane One-Dimensional Coordination Polymer as a Multi-responsive Luminescence Sensor and Photocatalyst for Dye Degradation. Journal of Coordination Chemistry,77(5-6), 466-489, 2024. https://doi.org/10.1080/00958972.2024.2329941.
34.   R. F. Li, C. Huang, Y. T. Hong, M. J. Tian, and B. X. Zhu, Zn (II) and Cu (II) complexes constructed from a Schiff base macrocycle: Synthesis, vapor adsorption and photocatalytic degradation properties. Journal of Molecular Structure, 1327, 141222, 2025. https://doi.org/10.1016/j.molstruc.2024.141222.
35.   A. A. Essawy, A. M. Nassar and W. A. Arafa, A novel photocatalytic system consists of Co (II) complex@ ZnO exhibits potent antimicrobial activity and efficient solar-induced wastewater remediation. Solar Energy, 170, 388-397, 2018. https://doi.org/10.1016/ j.solener.2018.05.073.