Synthesis, Structural Analysis and Comparison with Theoretical Calculations of Heterocyclic Disperse Diazo Dyes

Year 2025, Volume: 29 Issue: 2, 407 - 414, 25.08.2025

Aykut Demirçalı

Abstract

The interest in azo dyes is increasing in the textile and dye industry. Along with this interest, in addition to experimental studies, quantum mechanical calculations have recently been frequently encountered in the literature. In the content of the study, first of all, three azo dyes were synthesized. Then, the characteristic properties of the compounds were determined experimentally using FT-IR and 1H-NMR spectroscopies. Then, the compounds were optimized in the B3LYP/6-311+(d,p) basis set using density functional theory with the Gaussian16 program. Theoretically, FT-IR and 1H-NMR values were calculated. It was observed that the experimental and theoretical results were compatible. In addition, the electronic properties of the azo dyes were investigated.

Keywords

Azo dye , Spektral analysis , Density Functional Theory

Heterosiklik Dispers Diazo Boyalarının Sentezi, Yapısal Analizi ve Teorik Hesaplamalarla Karşılaştırılması

Abstract

Azo boyar maddelere olan ilgi tekstil ve boya endüstrisinde giderek artmaktadır. Bu ilgiyle beraber, deneysel çalışmalara ek olarak kuantum mekaniksel hesaplamalara da son zamanlarda literatürde sıklıkla rastlanmaktadır. Çalışmanın içeriğinde öncelikle üç adet azo boyar madde sentezlenmiştir. Devamında bileşiklerin karakteristik özellikleri önce FT-IR ve 1H-NMR spektroskopileri kullanılarak deneysel olarak belirlenmiştir. Sonra Gaussian16 programıyla yoğunluk fonksiyonel teorisi kullanılarak bileşikler B3LYP/6-311G(d,p) baz setinde optimize edilmiştir. Teorik olarak, FT-IR ve 1H-NMR değerleri hesaplanmıştır. Deneysel ve teorik sonuçların uyumlu olduğu gözlenmiştir. Bunlara ilave olarak, azo boyar maddelerin electronik özellikleri incelenmiştir.

Keywords

Azo boyarmadde , Yapı analizi , Yoğunluk Fonksiyonel Teorisi

References

• [1] Said Benkhaya, Souad M'rabet, Ahmed El Harfi. 2020. Classifications, properties, recent synthesis and applications of azo dyes. Heliyon, 6, e03271.
• [2] L. Abd-Alredha, R. Al-Rubaie and R. Jameel Mhessn. 2012. Synthesis and Characterization of Azo Dye Para Red and New Derivatives, e-Journal of Chemistry, 9(1), 465-470.
• [3] Aykut Demirçalı, Adile Sarı. 2024. Five new heterocyclic disazo dyes derived from the 4-position: Synthesis, characterisation, and acute toxicity evaluation, Journal of Molecular Structure. 1313, 138707.
• [4] V. Selvaraj, T. Swarna Karthika, C. Mansiya, M. Alagar. 2021. An over review on recently developed techniques, mechanisms and intermediate involved in the advanced azo dye degradation for industrial applications, Journal of Molecular Structure. 1224, 129195.
• [5] Ehsan Ullah Mughal, Qandeel Alam Raja, Abdullah Yahya Abdullah Alzahrani, Nafeesa Naeem, Amina Sadiq, Ebru Bozkurt. 2023. Pyrimidine-based azo dyes: Synthesis, photophysical investigations, solvatochromism explorations and anti-bacterial activity, Dyes and Pigments. 220, 111762.
• [6] Kamalesh Verma, Gundappa Saha, Lal Mohan Kundu, Vikash Kumar Dubey. 2019. Biochemical characterization of a stable azoreductase enzyme from Chromobacterium violaceum: Application in industrial effluent dye degradation, International Journal of Biological Macromolecules. 121, 1011–1018.
• [7] Ozge Surucu, Serdar Abaci. 2018. Characterization and application of azo dye (E)-N-phenyl-4-(thiazole-2-yldiazenyl)aniline (PDA) for biomedical sterilization, Journal of the Mechanical Behavior of Biomedical Materials. 77, 408–413.
• [8] Durga Prasad Mishra, Prafulla Kumar Sahu, Biswajeet Acharya, Satya Prasad Mishra, Seturam Bhati. 2024. A review of the synthesis and application of azo dyes and metal complexes for emerging antimicrobial therapies, Results in Chemistry. 10, 101712.
• [9] Omer Kayir, Sevil Ozkinali. 2025. Synthesis, spectroscopic characterization and dyeing properties of new metal complexed azo dyes derived from gallic acid, Journal of Molecular Structure. 1327,141144.
• [10] M.A. Castro, F.J. Pereira, A.J. Aller, D. Littlejohn. 2020. Raman spectrometry as a screening tool for solvent-extracted azo dyes from polyester-based textile fibres, Polymer Testing. 91, 106765.
• [11] Alaa Z. Omar, Sara I. Nabil, Ezzat A. Hamed, Hussam Y. Alharbi, Majed S. Aljohani, Mohamed A. El-Atawy. 2025. Synthesis, characterization, and color performance of bis-azo and bis-pyrazole derivatives for dyeing of polyester, Journal of Molecular Structure. 1322, 140474.
• [12] Ghulam Shabir, Jiawan Su, Aamer Saeed, and Anwar Ul-Hamid. 2021. New Heterocyclic Azo Dyes: Design, Synthesis, and Application on Leather, Fibers and Polymers. Vol.22, No.12, 3385-3392.
• [13] Ghulam Hussain, Makshoof Ather, Misbah Ul Ain Khan, Aamer Saeed, Rashid Saleem, Ghulam Shabir, Pervaiz Ali Channar. 2016. Synthesis and characterization of chromium (III), iron (II), copper (II) complexes of 4-amino-1-(p-sulphophenyl)-3-methyl-5-pyrazolone based acid dyes and their applications on leather, Dyes and Pigments. 130, 90-98.
• [14] H. Motiei, A. Jafari, R. Naderali. 2017. Third-order nonlinear optical properties of organic azo dyes by using strength of nonlinearity parameter and Z-scan technique, Optics & Laser Technology. 88, 68–74.
• [15] Rana Forsati, Sara Valipour Ebrahimi, Keivan Navi, Ezeddin Mohajerani, Hossein Jashnsaz. 2013. Implementation of all-optical reversible logic gate based on holographic laser induced grating using azo-dye doped polymers, Optics &LaserTechnology. 45, 565–570.
• [16] C. Karaca, A. Atac, M. Karabacak. 2015. Quantum chemical calculation (electronic and topologic) and experimental (FT-IR, FT-Raman and UV) analysis of isonicotinic acid N-oxide Spectrochim. Acta A 140, 85–95.
• [17] Cramer, C.J., Truhlar, D.G. 2009. Density functional theory for transition metals and transition metal chemistry Phys. Chem. Chem. Phys. 11, 10757–10816.
• [18] Tachibana, M., Tanak, S., Yamashita, Y. Yoshizawa, K. J. 2002. Small Band-Gap Polymers Involving Tricyclic Nonclassical Thiophene as a Building Block. Phys. Chem. B. 106, 3549–3556.
• [19] Pai, C.-L., Liu, C.-L., Chen, W.-C., Jenekhe, S.A. 2006. Electronic structure and properties of alternating donor–acceptor conjugated copolymers: 3, 4-Ethylenedioxythiophene (EDOT) copolymers and model. Polymer. 47, 699–708.
• [20] Zade, S.S., Bendikov, M. 2006. From Oligomers to Polymer: Convergence in the HOMO−LUMO Gaps of Conjugated OligomersOrg. Lett. 8, 5243–5246.
• [21] Becke, A.D. 1988. Density-functional exchange-energy approximation with correct asymptotic behavior Phys. Rev. A. 38, 3098–3100. [22] Lee, C., Yang, W., Parr, R.G. 1988. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B. 37, 785–789.
• [23]Frisch, M.J., et.al. 2016. Gaussian 16, Revision B.01, Gaussian, Inc., Wallingford CT.
• [24] Dennington, R. Keith, T., Millam, J. GaussView, Version 6. Semichem Inc., Shawnee Mission, KS, 2016.
• [25] Moskovits, M., DiLella, D.P. 1980. Surface-enhanced Raman spectroscopy of benzene and benzene-d6 adsorbed on silver. J. Chem. Phys. 73, 6068–6075.
• [26] Moskovits, M., DiLella, D.P., Maynard, K.J. 1988. Surface Raman spectroscopy of a number of cyclic aromatic molecules adsorbed on silver: selection rules and molecular reorientation. Langmuir 4, 61–76.
• [27] Diwaker and Abhishek Kumar Gupta, 2014. Quantum Chemical and Spectroscopic Investigations of (Ethyl-4-hydroxy-3-((E)-(pyrenylimino) methyl) benzoate) by DFT Method, International Journal of Spectroscopy, 841593, 15.