Abstract
Charge transfer complex formation between 2-aminopyridine (2AP) as the electron donor with 2,5-dihydroxy-p-benzoquinone (AHBQ) as the π-electron acceptor has been investigated spectrophotometrically in acetonitrile (AN) and 50% acetonitrile + 50% 1,2-dichloroethane (V/V), (ANDC). The stoichiometry of the complex has been identified by Job’s method to be 1:1. The Benesi-Hildebrand equation has been applied to estimate the formation constant (K CT) and molecular extinction coefficient (ε). It was found that the value of K CT is larger in ANDC than in AN. The thermodynamic parameters are in agreement with the K CT values in that the enthalpy of formation (−ΔH) has a larger value in ANDC than in AN, suggesting higher stability of the complex in ANDC. The complex formed between 2AP and DHBQ has been isolated as a solid and characterized using elemental analysis, FTIR, and 1H NMR measurements. Moreover, it has been found that the formed complex involves proton transfer in addition to charge transfer.
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Gutmann, F., Johnson, H., Keyzer, H., Molnar, J.: Charge-Transfer Complexes in Biochemical Systems. Marcel Dekker, New York (1997)
Foster, R.: Organic Charge-Transfer Complexes. Academic Press, London/New York (1969)
Mulliken, R.S., Person, W.B.: Molecular Complexes. Wiley Interscience, New York (1969)
Bazzi, H.S., Moustafa, A., Alqaradawi, S.Y., Nour, E.M.: Synthesis and spectroscopic structural investigations of the charge transfer-complexes formed in the reaction of 2,6-diaminopyridine with π-acceptors TCNE, chloranil and DDQ. J. Mol. Struct. 842, 1–5 (2007)
Bazzi, H.S., Alqaradawi, S.Y., Moustafa, A., Nour, E.M.: Synthesis, spectroscopic and thermal studies of the reactions of the donors piperazine and N,N-dimethylpiperazine with σ- and π-acceptors. J. Mol. Struct. 879, 60–71 (2008)
Al-Attas, A.S., Habeeb, M.M., Al-Raimi, D.S.: Spectrophotometric determination of some amino heterocyclic donors through charge transfer complex formation with chloranilic acid in acetonitrile. J. Mol. Liq. 148, 58–66 (2009)
Al-Attas, A.S., Habeeb, M.M., Al-Raimi, D.S.: Synthesis and spectroscopic studies of charge transfer complexes between chloranilic acid and some heterocyclic amines in ethanol. J. Mol. Struct. 928, 158–170 (2009)
Sang, H.O., Bong, G.K., Sun, J.Y., Muchchintala, M., Ketack, K., Jung, Y.D.: The synthesis of symmetric and asymmetric perylene derivatives and their optical properties. Dyes Pigments 85, 37–42 (2010)
Joao, E.B., Agnaldo, D.G., Andre, L.B., Marco, A.D., Paoli, X.L., James, R.D., Ana, F.N.: A polymer gel electrolyte composed of a poly(ethylene oxide) copolymer and the influence of its composition on the dynamics and performance of dyesenstized solar cells. J. Power Sources 195, 1246–1255 (2010)
Barary, M.H., Abdel-Hay, M.H., Sabry, S.M., Belal, S.T.: Spectrofluorimetric determination of 2-aminopyridine as a potential impurity in piroxicam and tenoxicam with the pharmacopoeial limit. J. Pharm. Biomed. Anal. 34, 221–226 (2004)
Kirsch, G.E., Narahashi, T.: A potent new potassium channel blocker. Biophys. J. 22, 507–512 (1978)
Segal, J.I., Brunnemann, B.S.: 4-Aminopyridine improves pulmonary function in quadriplegic humans with longstanding spinal cord injury. Pharmacotherapy 17, 415–423 (1997)
Schwid, S.R., Petrie, M.D., McDermott, M.P., Tiemery, D.D., Manson, D.H., Goodman, A.D.: Quantitative assessment of sustained-release 4-aminopyridine for symptomatic treatment of multiple sclerosis. Neurology 48, 817–821 (1997)
Parfitt, K., Sweetman, S.C., Blake, P.S., Parsons, A.V.: Martindale, The Extra Pharmacopoeia, 32nd edn., pp. 80, 88. Pharmaceutical Press, London (1999)
Akyuz, S.: The FT-IR spectroscopic investigation of transition metal (II) 4-aminopyridine tetracyanonickelate complexes. J. Mol. Struct. 482, 171–174 (1999)
Abdel-Hamid, M.E., Abdel-Salam, M., Mahrous, M.S.: The use of 2,3-dichloro-5,6-dicyano-p-benzoquinone for the spectrophotometric determination of some cardiovascular drugs. Talanta 34, 670–672 (1987)
Job, P.: Advanced Physicochemical Experiments. Pitman, London (1964)
Benesi, H.A., Hildebrand, J.H.: A spectrophotometric investigation of the interaction of iodine with aromatic hydrocarbons. J. Am. Chem. Soc. 71, 2703–2707 (1949)
Ghoneim, N.: Study of the preferential solution of some betaine dyes in binary solvent mixtures. Spectrochim. Acta A 57, 1877–1884 (2001)
Lewis, G.N., Randall, M.: Thermodynamics, 2nd edn. McGraw-Hill, New York (1961) (revised by Pitzer, K.S., Brewer, L.)
Habeeb, M.M., Al-Wakil, H.A., El-Dissouky, A., Refat, N.M.: Solvation and temperature effects on the proton transfer equilibria between 2,5-dihydroxy-p-benzoquinone and amines. J. Chem. Res., Synop., 200–205 (2001)
Caballero, N.A., Melendez, F.J., Munoz, C., Nino, A.: Theoretical prediction of relative and absolute pKa values of aminopyridines. Biophys. Chem. 124, 155–160 (2006)
Irving, H.M., Freiser, H., West, T.: IUPAC Compendium of Analytical Nomenclature Definitive Rules. Pergamon Press, Oxford (1981)
Miller, J.C., Miller, J.N.: Statistics for Analytical Chemistry, 2nd edn. Ellis Horwood, Chichester (1988)
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Al-Ahmary, K.M., Habeeb, M.M. & Al-Solmy, E.A. Spectroscopic and Thermodynamic Studies on Charge Transfer Complex Formation between 2-Aminopyridine and 2,5-Dihydroxy-p-benzoquinone. J Solution Chem 39, 1264–1277 (2010). https://doi.org/10.1007/s10953-010-9591-0
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DOI: https://doi.org/10.1007/s10953-010-9591-0