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New fluorescent Schiff bases linked azo chromophore: synthesis, complex formation with Cu(II) and Ni(II) ions, characterization, X-ray, SEM and optical properties

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Abstract

Azo-aldehyde compound L (1) was prepared by coupling 4-ethylbenzenediazonium chloride ions with salicylaldehyde, and the subsequent azo-Schiff bases HL1 (2) and HL2 (3) were obtained by the condensation of compound L (1) with o-chloroaniline and p-chloroaniline, respectively. New azo-Schiff base ligands and their nickel(II) and copper(II) complexes (4–7) were also prepared and characterized by various analytical and spectroscopic methods, such as, elemental analysis and FTIR, GC–MS and NMR spectra. The metal complexes revealed the central metal atom as being coordinated to two phenolate oxygen atoms and two imine nitrogen atoms of two azo-Schiff bases, bearing approximate square-planar geometries. Further, spectral anaylyses data and metal-ion complexations revealed azo-hydrazone tautomerism within the two azo-Schiff bases HL1 (2) and HL2 (3). Azo-hydrazone tautomerism was evident through the formation of novel neutral mononuclear dye-metal complexes [M(L1)2] and [M(L2)2], with M=Cu(II) or Ni(II) and all the ligands being of the azo form. Characteristic evaluations of the dyes and their metal complexes were conducted using X-ray diffraction (XRD) and scanning electron microscopy/energy dispersive spectroscopy (SEM/EDX). XRD data revealed that the synthesized compounds were of crystalline structure. SEM studies showed that the surface morphologies of all the samples had different shapes and particle sizes. TGA studies were conducted for the thermal properties of the compounds synthesized. The ligands and the corresponding metal complexes displayed effective emissions upon UV irradiation. Ligands (1–3) showed 32, 38 and 35% quantum yields and 3.02, 3.57 and 3.30 ns excited-state lifetimes, respectively.

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References

  1. Merino E (2011) Synthesis of azobenzenes: The coloured pieces of molecular materials. Chem Soc Rev 40:3835–3853

    Article  CAS  PubMed  Google Scholar 

  2. Zhong X, Xiang L, Royer S, Valange S, Barrault J, Zhang H (2011) Degradation of C.I. Acid Orange 7 by heterogeneous Fenton oxidation in combination with ultrasonic irradiation. J Chem Technol Biotechnol 86:970–977

    Article  CAS  Google Scholar 

  3. Montazerozohori M, Jahromi SM (2012) Photocatalytic decolorization of ethyl orange at various buffer solutions using nano-titanium dioxide: a kinetic investigation. Desalin Water Treat 48:261–266

    Article  CAS  Google Scholar 

  4. Khanmohammadi H, Rezaeian K (2015) Solar-light induced photodecolorization of water soluble azo-azomethine dye: influence of operational parameters and nanophotocatalysts. Desalin Water Treat 55:655–663

    Article  CAS  Google Scholar 

  5. El-Ghamry HA, Alharbi BK, Takroni KM, Khedr AM (2023) A series of nanosized Cu(II) complexes based on sulfonamide azo dye ligands: An insight into complexes molecular structures, antimicrobial, antitumor and catalytic performance for oxidative dimerization of 2-aminophenol. Appl Organomet Chem 37:e6978

    Article  CAS  Google Scholar 

  6. Khedr AM, Gouda AA, El-Ghamry HA (2022) Nano-synthesis approach, elaborated spectral, biological activity and in silico assessment of novel nano-metal complexes based on sulfamerazine azo dye. J Mol Liq 352:118737–118752

    Article  CAS  Google Scholar 

  7. Khedr AM, El Ghamry HA, El-Sayed YS (2022) Nano-synthesis, solid state structural characterization, antimicrobial and anticancer assessment of new sulfafurazole azo dye-based metal complexes for further pharmacological applications. Appl Organomet Chem 36:e6548

    Article  CAS  Google Scholar 

  8. Saad FA, El-Ghamry H, Kassem MA, Khedr AM (2019) Nano-synthesis, biological efficiency and DNA binding affinity of new homo-binuclear metal complexes with sulfa azo dye based ligand for further pharmaceutical applications. J Inorg Organomet Polym Mater 29:1337–1348

    Article  CAS  Google Scholar 

  9. Khedr AM, El-Ghamry H, Kassem MA, Saad FA, El-Guesmi N (2019) Novel series of nanosized mono- and homobi-nuclear metal complexes of sulfathiazole azo dye ligand: Synthesis, characterization, DNA-binding affinity, and anticancer activity. Inorg Chem Commun 108:107496

    Article  CAS  Google Scholar 

  10. Lehn JM (1995) Supramolecular chemistry. Wiley-VCH, Wenham

    Book  Google Scholar 

  11. Basu Baul TS, Das P, Chandra AK, Mitra S, Pyke S (2009) The synthesis, characterization and structures of some 4-[((E)-1-{2-hydroxy-5-[(E)-2-(aryl)-1-diazenyl]phenyl} methylidene)amino]benzoic acid. Dyes Pigment 82:379–386

    Article  CAS  Google Scholar 

  12. Khanmohammadi H, Abdollahi A (2012) New diaminomaleonitrile-based azo-azomethine dyes; synthesis, characterization and spectral properties. Dyes Pigment 94:163–168

    Article  CAS  Google Scholar 

  13. Alemi AA, Shaabani B (2000) Synthesis and characterization of a Schiff base of p-tert-butylcalıx[4]arene and its complex with copper(II). Acta Chim Slov J 47:363–369

    CAS  Google Scholar 

  14. Kakanejadifard A, Azarbani F, Zabardasti A, Rezayat A, Ghasemian M, Kakanejadifard S (2013) Spectroscopic and solvatochromism studies along with antioxidant and antibacterial activities investigation of 2-((2-mercaptophenylimino)methyl)-4-(phenyldiazenyl)phenol. Spectrochim Acta A 114:404–409

    Article  CAS  Google Scholar 

  15. Ghasemian M, Kakanejadifard A, Azarbani F, Zabardasti A, Kakanejadifard S (2014) Spectroscopy and solvatochromism studies along with antioxidant and antibacterial activities investigation of azo–azomethine compounds 2-(2-hydroxyphenylimino)methyl)-4-phenyldiazenyl)phenol. Spectrochim Acta A 124:153–158

    Article  CAS  Google Scholar 

  16. Kakanejadifard A, Azarbani F, Zabardasti A, Kakanejadifard S, Ghasemian M, Esna-ashari F, Omidi S, Shirali S, Rafieefar M (2013) The synthesis, structural characterization and antibacterial properties of some 2-((4-amino-1,2,5-oxadiazol-3-ylimino)methyl)-4-(phenyldiazenyl)phenol. Dyes Pigment 97:215–221

    Article  CAS  Google Scholar 

  17. Berencén Y, Mundet B, Rodríguez JA, Montserrat J, Domínguez C, Garrido B (2017) Hotelectronengineeringforboostingelectroluminescenceefficiencies of silicon-richnitridelightemittingdevices. J Lumin 183:26–31

    Article  Google Scholar 

  18. Dumur F, Beouch L, Tehfe MA, Contal E, Lepeltier M, Wantz G, Graff B, Goubard F, Mayer CR, Lalevée J, Gigmes D (2014) Low-cost zinc complexes for white organic light-emitting devices. Thin Solid Films 564:351–360. https://doi.org/10.1016/j.tsf.2014.06.006

    Article  CAS  Google Scholar 

  19. Krucaite G, Tavgeniene D, Grazulevicius JV, Wang YC, Hsieh CY, Jou JH, Garsva G, Grigalevicius S (2014) 3,6-Diaryl substituted 9-alkylcarbazoles as hole transporting materials for various organic light emitting devices. Dyes Pigment 106:1–6

    Article  CAS  Google Scholar 

  20. So KH, Kim R, Park H, Kang I, Thangaraju K, Park YS, Kim JJ, Kwon S-K, Kim Y-H (2011) Synthesis and characterization of a new iridium (III) complex with bulky trimethylsilylxylene and applications for efficient yellow-green emitting phosphorescent organic light emitting diodes. Dyes Pigment 92:603–609

    Article  Google Scholar 

  21. Cho W, Sarada G, Park JS, Gal YS, Lee JH, Jin SH (2014) Synthesis and characterization of blue-emitting Ir(III) complexes with multi-functional ancillary ligands for solution-processed phosphorescent organic light-emitting diodes. Org Electron 15:2328–2336

    Article  CAS  Google Scholar 

  22. Deng Y, Niu W, Wang Z, Feng L (2017) Synthesis, photoelectric properties and application of a polymerfluorescent probe with quinoline and benzene groups. Sens Actuators B 238:613–618

    Article  CAS  Google Scholar 

  23. De Silva AP, Fox DB, Huxley AJM, McClenaghan ND, Roiron J (1999) Metal complexes as components of luminescent signalling systems. Coord Chem Rev 185–186:297–306

    Article  Google Scholar 

  24. Callan JF, de Silva AP, Magria DC (2005) Luminescent sensors and switches in the early 21st century. Tetrahedron 61:8551–8588

    Article  CAS  Google Scholar 

  25. Sıdır I, Sıdır YG, Berber H, Demiray F (2015) Emerging ground and excited state dipolemoments and external electric field effect on electronic structure. a solvatochromism and theoretical study on 2-((phenylimino)methyl)phenol derivatives. J Mol Liq 206:56–67

    Article  Google Scholar 

  26. Kurtoglu M, Serin S (2001) Synthesis and complex formation of Di[4-(11-chloro-3,6,9-trioxaundecyloxy)-phenylamino] glyoxime. Synth React Inorg Met Chem 31:1229–1237

    Article  CAS  Google Scholar 

  27. Kurtoglu M, Birbiçer N, Kimyonşen U, Serin S (1999) Determination of pKa values of some azo dyes in acetonitrile with perchloric acid. Dyes Pigment 41:143–147

    Article  CAS  Google Scholar 

  28. Kurtoğlu M (2004) Synthesis and characterization of new trinuclear vic dioxime complexes with Ni(II) and Cu(II) Ions. Synth React Inorg Met Chem 34:967–977

    Article  Google Scholar 

  29. Sarigul M, Kariper SE, Deveci P, Atabey H, Karakas D, Kurtoglu M (2017) Multi-properties of a new azo-Schiff base and its binuclear copper (II) chelate: preparation, spectral characterization, electrochemical, potentiometric and modeling studies. J Mol Struct 1149:520–529

    Article  CAS  Google Scholar 

  30. Kose M, Hepokur C, Karakas D, McKee V, Kurtoglu M (2016) Structural, computational and cytotoxic studies of square planar copper(II) complexes derived from dicyandiamide. Polyhedron 117:652–660

    Article  CAS  Google Scholar 

  31. Birbiçer N, Kurtoglu M, Serin S (1999) Synthesis of two new azo ligands containing polyoxyethylene glycol and their complexes with Ni(II), Cu(II) and Co(II). Synth React Inorg Met Chem 29:1353–1364

    Article  Google Scholar 

  32. Sahan F, Kose M, Hepokur C, Karakas D, Kurtoglu M (2019) New azo-azomethine-based transition metal complexes: synthesis, spectroscopy, solid-state structure, density functional theory calculations and anticancer studies. Appl Organomet Chem 33:1–13

    Article  Google Scholar 

  33. Guilbault GG (ed) (1990). Marcel Dekker, New York, USA

    Google Scholar 

  34. Gilbert A, Bagott J (1991) Essentials of molecular photochemistry. CRC Press Boca Raton Inc, Florida

    Google Scholar 

  35. Osaheni JA, Jenekhe SA (1995) Electroactive and photoactive rod-coil copolymers-design, synthesis, and supramolecular regulation of photophysical properties. J Am Chem Soc 117(7):7389–7398

    Article  CAS  Google Scholar 

  36. Sahin O, Albayrak C, Odabasoglu M, Buyukgungor O (2005) (E)-5-(4-ethylphenyl diazenyl) salicylaldehyde. Acta Cryst E61:o4154–o4155

    Google Scholar 

  37. Williams DH, Fleming I (1980) Spectroscopic methods in organic chemistry, 3rd edn. McGraw Hill, New York, p 49

    Google Scholar 

  38. Eren T, Kose M, Kurtoglu N, Ceyhan G, McKee V, Kurtoglu M (2015) An azo-azomethine ligand and its copper(II) complex: synthesis, X-ray crystal structure, spectral, thermal, electrochemical and photoluminescence properties. Inorganica Chim Acta 430:268–279

    Article  CAS  Google Scholar 

  39. Khanmohammadi H, Darvishpour M (2011) Copper(II) complexes of pyridazine-based azo-azomethine ligands: synthesis, characterization thermal and absorption properties. J Inorg Organomet Polym Mater 21:541–546

    Article  CAS  Google Scholar 

  40. Chen X-C, Tao T, Wang Y-G, Peng Y-X, Huang W, Qian H-F (2012) Azo-hydrazone tautomerism observed from UV-vis spectra by pH control and metal-ion complexation for two heterocyclic disperse yellow dyes. Dalton Trans 41:11107–11115

    Article  CAS  PubMed  Google Scholar 

  41. Suryanarayana C, Grant Norton M (1998) X-ray diffraction: a practical approach. PlenumPress, New York, p 207

    Google Scholar 

  42. Arish D, Sivasankaran Nair M (2011) Synthesis, spectroscopic, antimicrobial, DNA binding and cleavage studies of some metal complexes involving symmetrical bidentate N, N donor Schiff base ligand. Spectrochim Acta A 82:191–199

    Article  CAS  Google Scholar 

  43. Varnes AW, Dodson RB, Wehry EL (1972) Interactions of transition-metal ions with photoexcited states of flavins. Fluorescence quenching studies. J Am Chem Soc 94:946–950

    Article  CAS  PubMed  Google Scholar 

  44. Kemlo JA, Shepherd TM (1977) Quenching of excited singlet states by metal ions. Chem Phys Lett 47:158–162

    Article  CAS  Google Scholar 

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Acknowledgements

Authors thank the Research Foundation of Kahramanmaras Sutcu Imam University, Kahramanmaras, Turkey, for the financial support (Project No: 2011/8-5 YLS). Also the authors are grateful to the Departments of Chemistry at Kahramanmaras Sutcu Imam University, Gaziantep University and Loughborough University for providing the laboratory and analytical facilities.

Funding

Research Foundation of Kahramanmaras Sutcu Imam University, Kahramanmaras, Turkey (Project No: 2011/8-5 YLS).

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, Kahramanmaras Sutcu Imam University, 46050, Kahramanmaras, Turkey

    Gözde Özkan & Mukerrem Kurtoglu

  2. Department of Physics, Faculty of Science, Kahramanmaras Sutcu Imam University, 46050, Kahramanmaras, Turkey

    Celal Kursun

  3. Department of Chemistry, Faculty of Science and Literature, Gaziantep University, 27310, Gaziantep, Turkey

    Huseyin Zengin & Gulay Zengin

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  1. Gözde Özkan
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Contributions

GÖ contributed to Investigation and Methodology; CK contributed to Investigation, Visualization, Data curation; HZ contributed to Software, Investigation, Data curation, Visualization, Writing—Review; GZ contributed to Writing—Review & Editing; MK contributed to Project administration, Methodology, Data curation, Supervision, Writing—Original Draft, Writing—Review & Editing. All authors reviewed the manuscript.

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Correspondence to Mukerrem Kurtoglu.

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Özkan, G., Kursun, C., Zengin, H. et al. New fluorescent Schiff bases linked azo chromophore: synthesis, complex formation with Cu(II) and Ni(II) ions, characterization, X-ray, SEM and optical properties. Transit Met Chem 48, 143–155 (2023). https://doi.org/10.1007/s11243-023-00531-0

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