Preparation and Spectroscopic Studies of Cadmium(II), Zinc(II),Mercury(II) and Vanadium(IV) Chelates Azo Ligand Derived from 4-Methyl-7-hydroxycoumarin

Bayader Fathil Abass(1), Taghreed Mohy Al-Deen Musa(2), Mahmoud Najim Aljibouri(3*)

(1) Department of Chemistry, College of Science, Mustansiriyah University, Baghdad, Iraq
(2) Department of Chemistry, College of Science, Mustansiriyah University, Baghdad, Iraq
(3) Department of Chemistry, College of Science, Mustansiriyah University, Baghdad, Iraq
(*) Corresponding Author


The present paper demonstrates the synthesis and characterization of some transition elements complexes derived from (E)-7-hydroxy-6-((4-methoxyphenyl)diazenyl)-4-methyl-2H-chromen-2-one. The ligand was prepared in the general route of azo dyes by coupling the diazonium salt of 4-methoxyaniline with 4-methyl-7-hydroxycoumarin in sodium hydroxide 10% (w/v) solution. The azo ligand was identified on the basis of elemental analyses, MS, H-NMR and FT-IR spectra. The products of complexes with the new azo dye were isolated by the direct reactions of the metal chlorides of cadmium(II), zinc(II), vanadium(IV) and mercury(II) ions with the alkaline solution of free ligand to afford the colored in the following formulas, complexes[ML2]2H2O formula, M=Cd(II) and Zn(II). However the vanadium(IV) complex was square pyramid in [VOL2]SO42H2O chemical formula. As well as the tetrahedral environment was suggested for mercury(II) complex in formula [HgL2]. The time and mole ratio factors were studied to obtain the optimized conditions of metal complexes formations and the observed data investigated the deprotonation of the azo-dye at pH to range (7–7.5) with 30 min as time of reaction to get pure metal chelates. The TG-DSC study confirmed the thermal stability of complexes at a wide range of average heating in inert gas of analysis and the results observed from loss weight percent investigated the proposed structures of the prepared metal complexes.


azo ligands; metal complexes of coumarin; spectroscopic studies

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[1] Gao, P., Tsao, H.N., Yi, C., Grätzel, M., and Nazeeruddin, M.K., 2014, Extended π‐bridge in organic dye‐sensitized solar cells: The longer, the better?, Adv. Energy Mater., 4 (7), 1301485.

[2] Tsuzuki, K., and Tada, M., 1986, The syntheses of pteridin-2-one derivatives from diaminomaleonitrile (DAMN), J. Heterocycl. Chem., 23 (5), 1299–1301.

[3] Ayare, N.N., Ramugade, S.H., and Sekar, N., 2019, Photostable coumarin containing azo dyes with multifunctional property, Dyes Pigm., 163, 692–699.

[4] Tathe, A.B., and 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.

[5] Matsumura, K., Yoshizaki, S., Maitani, M.M., Wada, Y., Ogomi, Y., Hayase, S., Kaiho, T., Fuse, S., Tanaka, H., and Takahashi, T., 2015, Rapid synthesis of thiophene-based, organic dyes for dye-sensitized solar cells (DSSCs) by a one-pot, four-component coupling approach, Chem. Eur. J., 21 (27), 9742–9747.

[6] Sahoo, J., and Paidesetty, S.K., 2015, Biological evaluation and spectral characterization of 4-hydroxy coumarin analogues, J. Taibah Univ. Med. Sci., 10 (3), 306–319.

[7] Cigáň, M., Donovalová, J., Szöcs, V., Gašpar, J., Jakusová, K., and Gáplovský, A., 2013, 7-(Dimethylamino)coumarin-3-carbaldehyde and its phenylsemicarbazone: TICT excited state modulation, fluorescent H-aggregates, and preferential solvation, J. Phys. Chem. A, 117, 4870–4883.

[8] Wang, S., Shen, S., and Xu, H., 2000, Synthesis, spectroscopic and thermal properties of a series of azo metal chelate dyes, Dyes Pigm., 44 (3), 195–198.

[9] Refat, M.S., EI-Sayed, M.Y., and Adam, A.M.A., 2013, Cu(II), Co(II) and Ni(II) complexes of new Schiff base ligand: Synthesis, thermal and spectroscopic characterizations, J. Mol. Struct.,1038, 62–72.

[10] Sahoo, J., Mekap, S.K., and Paidesetty, S.K., 2015, Synthesis, spectral characterization of some new 3-heteroaryl azo 4-hydroxy coumarin derivatives and their antimicrobial evaluation, J. Taibah Univ. Sci., 9 (2), 187–195.

[11] Satyanarayana, B., Muralikrishna, P., Kumar, D.R., and Ramachandran, D., 2013, Preparation and biological evaluation of phenothiazine derivatives, J. Chem. Pharm. Res., 5 (5), 262–266.

[12] Chetioui, S., Zouchoune, B., Merazig, H., Bouaoud, S.E., Rouag, D.A., and Djukic, J.P., 2021, Synthesis, spectroscopic characterization, crystal structure and theoretical investigation of two azo-palladium(II) complexes derived from substituted (1-phenylazo)-2-naphtol, Transition Met. Chem., 46, 91–101.

[13] Al-Jibouri, M.N., 2014, Synthesis and characterization of transition metal complexes with Azop ligand derived from 4-hydroxy-6-methyl-2-pyranone, Eur. Chem. Bull., 3 (5), 447–451.

[14] Freedman, D.A., Keresztes, I., and Asbury, A.L., 2002, Metal–coumarin complexes: Synthesis and characterization of 7-isocyanocoumarin ligands and Mo(CO)4(7-isocyanocoumarin)2 complexes. X-ray crystal structure of Mo(CO)4(7-isocyano-4-trifluoromethylcoumarin)2, J. Organomet. Chem., 642 (1), 97–106.

[15] Geary, W.J., 1971, The use of conductivity measurements in inorganic solvents for the characterization of coordination compounds, Coord. Chem. Rev., 7 (1), 81–122.

[16] Nithya, P., Rajamanikandan, R., Simpson, J., Ilanchelian, M., and Govindarajan, S., 2018, Solvent assisted synthesis, structural characterization and biological evaluation of cobalt(II) and nickel(II) complexes of Schiff bases generated from benzyl carbazate and cyclic ketones studies, Polyhedron, 145, 200–217.

[17] Al‐Hamdani, A.A.S., and Al Zoubi, W., 2015, New metal complexes of N3 tridentate ligand: Synthesis, spectral studies, and biological activity, Spectrochim. Acta, Part A, 137, 75–89.

[18] Silverstein, R.M., Webster, X.F., and Kiemle, D.J., 2005, Spectrometric Identification of Organic Compounds, 7th Ed., John Wiley & Son, Inc., Hoboken, New York.

[19] Lu, L., Wang, J., Chen, F., Wei, L.T., Lin, L.M., Li, B.H., Singh, A., and Kumar, A., 2019, Structures and photocatalytic performance of two d10 metal-based coordination polymers containing mixed building units, Transition Met. Chem., 44 (2), 107–114.

[20] Esmaeilzadeh, M.A., 2019, Composite prepared from a metal-organic framework of type MIL-101(Fe) and morin-modified magnetite nanoparticles for extraction and speciation of vanadium(IV) and vanadium(V), Microchim. Acta, 186, 14.

[21] Kostova, I., Bhatia, S., Grigorov, P., Balkansky, S., Parmar, V.S., Prasad, A.K., and Saso, L., 2011, Coumarins as antioxidants, Curr. Med. Chem., 18 (25), 3929–3951.

[22] Białek, M., Fryga, J., Spaleniak, G., and Żołnowska, M., 2017, Synthesis and olefin homo- and copolymerization behavior of new vanadium complexes bearing [OSSO]-type ligands, React. Kinet., Mech. Catal., 122 (1), 259–273.


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