Abstract
Four novel metal(II) complexes, Ni(L)2, Co(L)2, Cu(L)2, and Zn(L)2 (L = 5-(2-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)hydrazono)-1,3-diethyl-2-thioxo-dihydropyrimidine-4,6(1H,5H)-dione), were synthesized using the procedure of diazotization, coupling and metallization. Their structures were identified by elemental analyses, 1H NMR, ESI-MS and FT-IR spectra. The effect of different central metal(II) ions on absorption bands of the metal(II) complexes was researched. The thermal properties of the metal(II) complexes were investigated by thermogravimetry (TG) and differential scanning calorimetry (DSC). Furthermore, the thermodynamic parameters, such as activation energy (E*), enthalpy (∆H*), entropy (∆S*) and free energy of the decomposition (∆G*) are calculated from the TG curves applying Coats–Redfern method. The results show that the metal(II) complexes have suitable electronic absorption spectra with blue-violet light absorption at about 350–450 nm, high thermal stability with sharp thermal decomposition thresholds.
Similar content being viewed by others
References
Kuwahara M, Takehara S, Kashihara Y, Watabe K, Nakano T, Tanaka M, et al. Experimental study of high-density rewritable optical disk using a blue-laser diode. Jpn J Appl Phys. 2003;42:1068–71.
Chang D, Yoon D, Ro M, Park I, Shin D. Synthesis and characteristics of protective coating on thin cover layer for high density-digital versatile disc. Jpn J Appl Phys. 2003;42:754–8.
Huang FX, Wu YQ, Gu DH, Gan FX. Spectroscopic and thermal properties of short wavelength metal (II) complexes containing α-isoxazolylazo-β-diketones as co-ligands. Spectrochim Acta A. 2005;61:2856–60.
Park H, Kim ER, Kim DJ, Lee H. Synthesis of metal-azo dyes and their optical and thermal properties as recording materials for DVD-R. Bull Chem Soc Jpn. 2002;75:2067–70.
Chen ZM, Wu YQ, Gu DH, Gan FX. Nickel(II) and copper(II) complexes containing 2-(2-(5-substitued isoxazol-3-yl)hydrazono)-5,5-dimethylcyclohexane- 1,3-dione ligands: synthesis, spectral and thermal characterizations. Dye Pigment. 2008;76:624–31.
Wang S, Shen S, Xu H. Synthesis, spectroscopic and thermal properties of a series of azo metal chelate dyes. Dye Pigment. 2000;44:195–8.
Wu SJ, Qian W, Xia ZJ, Zou YH, Wang SQ, Shen SY, et al. Investigation of third-order nonlinearity of an azo dye and its metal-substituted compounds. Chem Phys Lett. 2000;330:535–40.
Abe T, Mano S, Yamada Y, Tomotake A. Thermal dye transfer printing with chelate compounds. J Imaging Sci Technol. 1999;43:339–44.
Gup R, Gizioglu E, Kırkan B. Synthesis and spectroscopic properties of new azo-dyes and azo-metal complexes derived from barbituric acid and aminoquinoline. Dye Pigment. 2007;73:40–6.
Karcı F, Karcı F. The synthesis and solvatochromic properties of some novel heterocyclic disazo dyes derived from barbituric acid. Dye Pigment. 2008;77:451–6.
Song HF, Chen KC, Tian H. Synthesis of novel dyes derived from 1-ethyl-3-cyano-6-hydroxy-4-methyl-5-amino-2-pyridone. Dye Pigment. 2002;53:257–62.
Kirkan B, Gup R. Synthesis of new azo dyes and Copper(II) complexes derived from barbituric acid and 4-aminobenzoylhydrazone. Turk J Chem. 2008;32:9–17.
Christie RM, Dryburgh WT, Standring PN. Some monoazoacetoacetanilide pigments derived from heterocyclic diazo components. Dye Pigment. 1991;16:231–40.
El-Boraey HA, El-Saied FA, Aly SA. UO2(VI), Sn(IV), Th(IV) and Li(I) complexes of 4-azomalononitrile antipyrine. J Therm Anal Calorim 2009;96:599–606. doi:10.1007/s10973-008-9197-6.
Karcı F, Karcı F. Synthesis and absorption spectra of some novel heterocyclic disazo dyes derived from pyridone and pyrazolone derivatives. Dye Pigment. 2008;76:147–57.
Ertan N, Gürkan P. Synthesis and properties of some azo pyridone dyes and their Cu(II) complexes. Dye Pigment. 1997;33:137–47.
Peng Q, Li M, Gao K, Cheng L. Hydrazone-azo tautomerism of pyridone azo dyes: Part 1—NMR Spectra of Tautomers. Dye Pigment. 1990;14:89–99.
Bâtiu C, Panea I, Ghizdavu L, David L, Ghizdavu Pellascio S. Divalent transition metal complexes 4-(4-ethoxy-phenylhydrazono)-1-phenyl-3-methyl-1H-pyrazolin-5 (4H)-one . J Therm Anal Calorim. 2005;79:129–34.
Peng Q, Li M, Gao K, Cheng L. Hydrazone-azo tautomerism of pyridone azo dyes: Part III—effect of dye structure and solvents on the dissociation of pyridone azo dyes. Dye Pigment. 1992;18:271–86.
Issa RM, Khedr AM, Rizk HF. UV–vis, IR and 1H NMR spectroscopic studies of some Schiff bases derivatives of 4-aminoantipyrine. Spectrochim Acta A. 2005;62:621–9.
Ropret P, Centeno SA, Bukovec P. Raman identification of yellow synthetic organic pigments in modern and contemporary paintings: reference spectra and case studies. Spectrochim Acta A. 2008;69:486–97.
Abdel-Latif SA, Hassib HB. Studies of Mn(II), Co(II), Ni(II) and Cu(II) Chelates with 3-phenyl-4-(p-methoxy-phenylazo)-5-pyrazolone. J Therm Anal Calorim. 2002;68:983–95.
Garg BS, Sharma RK, Kundra E. Copper(II), nickel(II), cobalt(II) and zinc(II) complexes of 2-[2-(6-methylbenzothiazolyl)azo]-5-dimethylaminobenzoic acid: synthesis, spectral, thermal and molecular modelling studies. Transition Met Chem. 2005;30:552–9.
Omar MM, Mohamed GG. Potentiometric, spectroscopic and thermal studies on the metal chelates of 1-(2-thiazolylazo)-2-naphthalenol. Spectrochim Acta A. 2005;61:929–36.
Xu G-C, Zhang L, Liu L, Liu G-F, Jia D-Z. Kinetics of thermal decomposition of mixed-ligand nikkel(II) and copper(II) complexes of 4-acyl pyrazolone derivative and pyridine. J Therm Anal Calorim. 2007;89:547–53.
Griffiths J, Translated by Hou YF, Wu ZW, Hu JZ. Colour and constitution of organic molecules. Beijing: Chemistry Industry Press; 1985. p. 202.
Snavely FA, Suydam FH. Notes- structure of aryl azo pyrozolone compounds and their copper derivatives. J Org Chem. 1959;24:2039–40.
Zaitev BE, Zaiteva VA, Molodkin AK, Obraztova ES. Synthesis and the structure of 1-phenyl-3-methyl-4-phenylazopyrazol-5-one with Cu(ІІ) and Co(ІІ). Zh Neorg Khim. 1979;24:127–33.
Coat AW, Redfern JP. Kinetic parameters from thermogravimetric data. Nature. 1964;201:68–9.
Kandil SS, El-Hefnawy GB, Baker EA. Thermal and spectral studies of 5-(phenylazo)-2-thiohydantoin and 5-(2-hydroxyphenylazo)-2-thiohydantoin complexes of cobalt(II), nickel(II) and copper(II). Thermochim Acta. 2004;414:105–13.
Acknowledgements
Financial support from the National Natural Science Foundation of China (No. 60490290), Chinese Academy of Sciences (KJCX2.YW.M06) and the National Science and Technology Program of China (No. 2007AA03Z412) is gratefully acknowledged.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Li, X., Wu, Y., Gu, D. et al. Synthesis, spectral and thermal properties of some transition metal(II) complexes with a novel ligand derived from thiobarbituric acid. J Therm Anal Calorim 98, 387–394 (2009). https://doi.org/10.1007/s10973-009-0290-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10973-009-0290-2