Dinuclear Copper(II) Complex of Containing N,N-diisopropyl,N'-3-propylamide-ethylenediamine, and Dihydroxo Bridge; Solvatochromic and Thermochromic

Document Type : Research Article


Department of Chemistry, University of Mazandaran, Babolsar, I.R. IRAN


The synthesis and characterization of a dinuclear [LCu(m-OH)2CuL](ClO4)2, complex with a tridentate N,N-diisopropyl,N'-3-propylamide-ethylenediamine hemilabile ligand (abbreviated L) is reported. The dinuclear complex was characterized by elemental analysis, molar conductance, thermal analysis, and spectral studies. In the complex, both copper centers are 5-coordinated and bridged through two hydroxo groups.  Thermo- and solvatochromic behaviors of the complex were investigated by visible spectroscopy. Its reversible thermochromism (blue ↔ green) in acetonitrile solution is due to dissociation and re-coordination of Cu-O(amide) moiety. The solvent-dependent absorption maxima, lmax, was studied by a Stepwise Multiple Linear Regression (SMLR) analysis to determine the best model describing the resulting positive solvatochromism.  The statistical results demonstrated that among different solvent parameters, Donor Number (DN) is a dominant parameter that is responsible for the redshift in the d-d absorption band of the complex by increasing its values.


Main Subjects

[1] Tabacco M.B., Uttamlal M., McAllister M., Walt D.R., An Autonomous Sensor and Telemetry System for Low-level pCO2 Measurements in Seawater, Anal. Chem., 71(1): 154-161 (1999).
[2] Gou M., Guo G., Zhang, J.A., Men K., Song J., Luo F., Zhao X., Qian Z., Wei Y.Q., Time-Temperature Chromatic Sensor Based on Polydiacetylene (PDA) Vesicle and Amphiphilic Copolymer, Sensor Actuat B-Chem 150(1): 406-411 (2010).
[5] Sato O., Hayami S., Einaga Y., Gu Z.Z., Control of the Magnetic and Optical Properties in Molecular Compounds by Electrochemical, Photochemical and Chemical Methods, Bull. Chem. Soc. Jpn., 76(3): 443-470 (2003).
[8] Sone K, Fukuda Y. “Ions and Molecules in Solution”, Elsevier, Amsterdam (1983).
[10] Linert W., Fukuda Y., Camard A., Chromotropism of Coordination Compounds and its Applications  in Solution, Coord. Chem. Rev., 218: 113-152 (2001).
[11] Miao J., Nie Y., Xiong Z., Chai Y., Fu S., Yan H., Stimulus-responsive Reversible Thermochromism and Exciplex Emission of a Zn(II) Complex and Selective Sensing of NH3 Gas, Dalton T, 48(15): 5000-5006 (2019).
[14] Méndez-Arriaga J. M., Oyarzabal I., Martín-Montes Á., García-Rodríguez J., Quirós M., Sánchez-Moreno M., First Example of Antiparasitic Activity Influenced by Thermochromism: Leishmanicidal Evaluation of 5, 7-dimethyl-1, 2, 4-triazolo [1, 5-a] pyrimidine Metal Complexes. Med. l Chem., 16(3): 422-430 (2020).
[15] Kazemi S., Golchoubian H. Structure and Chromotropic Properties of 2-Picolylamine-Ni (II) Complex. Inorg. Chem. Res., 4(1):76-85 (2020).
[17] Aryannezhad M., Behmadi H., Saadati S.M., Poormorteza N., Amini Moghaddam Z., Synthesis and Characterization of Novel Photoactive‎ Poly (ether-amide) Based on Highly Substituted‎ Phenanthrimidazole, Iran. J. Chem. Chem. Eng. (IJCCE), 36(6): 69-76 (2017).
[18] Nurchi V.M., Crisponi G., Sanna G., Pérez-Toro I., Niclos-Gutierrez J., Gonzalez-Perez M.J., Martín A.D., Complex Formation Equilibria of Polyamine lLigands with Copper (II) and Zinc (II), J. Inorg. Biochem, 194: 26-33 (2019).
[19] Fukuda Y., “Inorganic Chromotropism”, Springer, Berlin (2007).
[20] Chao M.-S., Lu H.-H., Tsai M.-L., Huang S.-L., Hsieh T.-H., Reversible Switching of Coordination Modes of Nickel (ΙΙ) Complexes Using a Hemilabile 4,7-diazadecanediamide Ligand, Inorg. Chim. Acta, 362(10): 3835–3839 (2009).
[22] Golchoubian H., Tarahomi M., Rezaee E., Bruno G., Synthesis, Structural Characterization and Chromotropism of a Copper(II) Complex Containing Bidentate Ligand, Polyhedron, 85: 635–642 (2015).
[24] Koohzad S., Golchoubian H., Jagličić Z., Structural, Solvatochromism and Magnetic Properties of Two Halogen Bridged Dinuclear Copper (II) Complexes: a Density Functional Study, Inorg. Chim. Acta, 473: 60–69 (2018).
[25] SPSS/PS, “Statistical Package for IBMPC”, Quiad Software Version 13, Ontario, (1998).
[26] Darlington R. B., “Regression and Linear Models”, McGraw-Hill, New York (1990).
[27] Riahi S., Mousavi M. F., Shamsipur M., Prediction of Selectivity Coefficients of a Theophylline-Selective Electrode Using MLR and ANN, Talanta 69(3): 736-740 (2006).
[30] Meek D. E., Ehrhardt S. A., Copper(II) Complexes of Secondary and Tertiary N-substituted Ethylenediamines, Inorg. Chem., 4(4): 584-587 (1965).
[31] Raman N., Esthar S., Thangaraja C., A New Mannich base and its Transition Metal(II) Momplexes- Synthesis, Mtructural Characterization and Electrochemical Study, J. Chem. Sci., 116(4): 209-213 (2004).
[32] Nakamoto K., Ohkaku N., Metal Isotope Effect on Metal-Ligand Vibrations. VI. Metal Complexes of 8-hydroxyquinoline, Inorg. Chem., 10(4): 798-805 (1971).
[34] Banerjee S., Mondal S., Chakraborty W., Sen S., Gachhui R., Butcher R. J., Slawin A. M. Z., Mandal C., Mitra S., Syntheses, X-ray Crystal Structures, DNA Binding, Oxidative Cleavage Activities and Antimicrobial Studies of Two Cu (II) Hydrazone ComplexesPolyhedron, 28(13): 2785-2793 (2009).
[35] Lever A. B. P., “Inorganic Electronic Spectroscopy”, 2nd ed., Elsevier Science, Amsterdam (1984).
[38] Hadjmohammadi M.R., Chaichi M.J., Yousefpour M., Solvatochromism Effect of Different Solvents on UV-Vis Spectra of Flouresceine and its Derivatives, Iran. J. Chem. Chem Eng (IJCCE). 27(4): 9-14 (2008)
[39] Erdal Tümer, A., Edebali, S., Gülcü, Ş., Modeling of Removal of Chromium (VI) from Aqueous Solutions Using Artificial Neural Network, Iran. J. Chem. Chem Eng (IJCCE)., 39(1): 163-175 (2020).