Abstract
New 5-pyrazolone based azo- dyes (2–5) and a bisazo- dye (6) were synthesized via diazo- coupling reaction with substituted aryl amines. All azo-5-pyrazolone compounds were characterized with the aid of FTIR, UV-Vis., 1H NMR, 13C NMR-APT and, GC-MS or ESI(+)-MS spectroscopic techniques. NMR studies showed that all azo- and bisazo- compounds, are in hydrazo-keto form except compound 5 which is in enol-azo form in solution. FTIR(ATR) studies indicated that compounds 2 and 4 are in azo-keto form, compounds 3 and 6 are in hydrazo-keto form and compound 5 is in enol-azo form in the solid state. All newly synthesized compounds were investigated for their absorption and emission characteristics. Photophysical properties of the solvent polarity effect and acid/base effect on the absorption and emission spectra were evaluated for an azo- (2) and a bisazo- compound (6). All azo-5-pyrazolone compounds showed fluorescence properties and the solvents with different polarities gave rise to shifts in the absorption and emission spectra of 2 and 6. The base addition did not affect the emission spectra while changing the absorption properties of the azo- and bisazo- compounds. Thermal work of 2 and 6 were carried out with TG/DTG technique and the results showed that compound 2 had adequate stability for industrial applications as a fluorescent material.
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References
Maas G (2009) New syntheses of diazo compounds. Angew Chem Int Ed 8186-8195
Stoilova A, Georgiev A, Nazarova D, Dimov D (2019) Structure-property relationship and photoinduced birefringence of the azo and azo-azomethine dyes thin films in PMMA matrix. Opt Mater 87:16–23
Mix KA, Aronoff MR, Raines RT (2019) Diazo compounds: versatile tools for chemical biology. ACS Chem Biol 11(12):3233–3244
Gunnlaugsson T, Leonard JP, Murray NS (2004) Highly selective colorimetric naked-eye cu(II) detection using an azobenzene chemosensor. Org Lett 6(10):1557–1560
Fuhrmann T, Salbeck J (2003) Organic materials for photonic devices. MRS Bull 28(5):354–359
Manuela M, Raposo M, Sousa Ana MRC, Mauricio A, Fonseca C, Kirsch G (2005) Thienylpyrrole azo dyes: synthesis, solvatochromic and electrochemical properties. Tetrahedron 61:8249–8256
Raposo MMM, Sousa AMRC, Fonseca AMC, Kirsch G (2005) Thienylpyrrole azo dyes: synthesis, solvatochromic and electrochemical properties. Tetrahedron 61:8249–8256
Piao W, Hanaoka K, Fujisawa T, Takeuchi S, Komatsu T, Ueno T, Terai T, Tahara T, Nagano T, Urano Y (2017) Development of an azo-based photosensitizer activated under mild hypoxia for photodynamic therapy. J A Chem Soc 139:13713–13719
Casas JS, Garcia-Tasende MS, Sanchez A, Sordo J, Touceda A (2007) Coordination modes of 5-pyrazolones: a solid-state overview. Coord Chem Rev 251:1561–1589
Deng Y, Jiang H, Ye D, Zhou R, Li H, Tang B, Jin M, Li N, Guo Y, Zhou G (2018) Synthesis and application of an alkylated pyrazole-based azo dye for electrofluidic display. J Soc Inf Display 26(6):369–375
Ghanadzadeh Gilani A, Taghvaei V, Moradi Rufchahi E, Mirzaei M (2019) Tautomerism, solvatochromism, preferential solvation, and density functional study of some heteroarylazo dyes. J Mol Liq 273:392–407
Constantinescu C, Matei A, Ionita I, Ion V, Marascu V, Dinescu M, Vasiliu C, Emandi A (2014) Azo-derivatives thin films grown by matrix-assisted pulsed laser evaporation for non linear optical applications. Appl Surf Sci 302:69–73
Tathe AB, Sekar N (2016) Red emitting coumarin-azo dyes: synthesis, characterization, linear and non-linear optical properties-experimental and computational approach. J Fluoresc 26(4):1279–1293
Bagdatli E, Akkus S, Yolacan C, Ocal N (2007) Sulfur-nitrogen heterocycles from the condensation of pyrazolones and 2-iminothiazolidin-4-ones with phenyl isothiocyanate. J Chem Res 5:302–304
Bagdatli E, Ocal N (2012) Synthesis, spectroscopic, and dyeing properties of new azo and bisazo dyes derived from 5-pyrazolones. J Het Chem 49(5):1179–1186
Gunkara OT, Bagdatli E, Ocal N (2013) Synthesis of new pyrazolone dyes. J Chem Res 4:227–231
Bagdatli E (2017) Evaluation of some 5-pyrazolone-based copper(II) complexes as catalysts for the oxidation of trans-stilbene. Chem Heterocycl Compd 53(8):861–866
Akama Y, Tong A (1996) Spectroscopic studies of the keto and enol tautomers of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone. Microchem J 53:34–41
Field LD, Sternhell S, Kalman JR (2007) Organic structures from spectra. John Wiley and Sons, Singapore
Saeed A, Shabir G, Mahar J, Irfan M (2015) Spectroscopic and electrochemical behavior of newly synthesized high fluorescent symmetric 40-nitrophenyl-3,4,9,10-perylenebisdiimide-azo hybrid dyes. Spectrochim Acta A Mol Biomo Spectrosc 151:72–79
Singh H, Sindhu J, Khurana JM, Sharmab C, Aneja KR (2014) Syntheses, biological evaluation and photophysical studies of novel 1,2,3-triazole linked azo dyes. RSC Adv 4:5915–5926
Steel C, Thomas TF (1966) The fluorescence of cyclic azo-compounds: determination of singlet lifetimes. Chem Commun 24:900–902
Williams RT, Bridges JW (1964) Fluorescence of solutions: a review. J Clin Path 17:371–394
Aksungur T, Arslan O, Seferoglu N, Seferoglu Z (2015) Photophysical and theoretical studies on newly synthesized N,N-diphenylamine based azo dye. J Mol Struct 1099:543–550
Coats AW, Redfern JP (1963) Thermogravimetric analysis: a review. Analyst 88:906–924
Brack H-P, Ruegg D, Buhrer H, Slaski M, Alkan S, Scherer GG (2004) Differential scanning calorimetry and thermogravimetric analysis investigation of the thermal properties and degradation of some radiation-grafted films and membranes. J Polym Sci Part B Polym Phys 42(13):2612–2624
Yang L, Zhang L, Chen J, Ren L, Zhu Y, Wang X, Yu X (2009) Study on the fluorescence and thermal stability of hybrid materials Eu(Phen)2Cl3/MCM-41. Front Chem China 4(2):149–153
Acknowledgments
We thank the Central Research Laboratory of Ordu University for GC-MS, TG-DTG, and Fluorimetric analyses. A part of this work was supported by Yıldız Technical University, Scientific Research Projects Coordination Department, Project number: YTUAF (2009-01-02-ODAP01).
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This work is dedicated to the lovely memory of Prof. Dr. Zehra Nuket Ocal Sunguroglu.
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Bagdatli, E., Yaman, D. Photophysical Properties of New Pyrazolone Based Azo- Compounds. J Fluoresc 30, 51–61 (2020). https://doi.org/10.1007/s10895-019-02469-y
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DOI: https://doi.org/10.1007/s10895-019-02469-y