232
R.M. Alghanmi et al. / Journal of Molecular Structure 1034 (2013) 223–232
[2] S.Y. Saad, T.A. Najjar, M.H. Daba, A.C. Al-Rikabi, Chemotherapy 48 (2002) 309–
315.
[3] E. Von Haxhausen, Pharmako 226 (1955) 163–171.
[4] G.G. Rowe, H.P. Gurtner, C.J. Chelius, S. Afonso, C.A. Castillo, C.W. Crumpton,
Proc. Soc. Exp. Biol. Med. 105 (1960) 98–100.
[5] W.S. Faraci, A.A. Nagel, K.A. Verdries, L.A. Vincent, H. Xu, L.E. Nichols, J.M.
Labasi, E.D. Salter, E.R. Pettipher, Br. J. Pharmacol. 119 (1996) 1101–1108.
[6] E.R. Pettipher, T.H. Hibbs, M.A. Smith, R.J. Griffiths, Inflamm. Res. 46 (1997)
S135–S136.
[7] R. Boer, W.R. Ulrich, T. Klein, B. Mirau, S. Haas, I. Baur, Mol. Pharmacol. 58
(2000) 1026–1034.
[8] S.P. Jose, S. Mohan, Spectrochim. Acta A 64 (2006) 240–245.
[9] R.S. Mulliken, J. Am. Chem. Soc. 72 (1950) 4493–4503.
[10] R.S. Mulliken, W.B. Pearson, Molecular Complexes, Wiley Publishers, New
York, 1969.
[11] R. Foster, Charge Transfer Complexes, Academic press, London, 1969.
[12] R.S. Mulliken, J. Phys. Chem. 56 (1952) 801–822.
[13] F.P. Fla, J. Palou, R. Valero, C.D. Hall, P. Speers, J. Chem. Perkin Trans. 2 (1991)
1925–1928.
bonding between the amino group of donor and hydroxyl group of
acceptor as can be seen in the energy minimized structure of the
complex. Also, the change of the wave numbers or intensities of
the other main vibration bands of the complex compared with
reactants confirms the formation of the charge transfer complex.
Hence, the formed complex included proton and charge transfer
which were responsible for its high stability. It is worthily to report
that the results of GAMESS calculations are in agreement with
those from infrared and 1H NMR data. A difference between the
1H NMR spectra is the disappearance of the second OH signal of
CLA although a band was assigned to OH stretching vibration in
the computed infrared spectra at 3806 cmꢂ1, the situation is
strongly connected with the high polarity of DMSO that led to
the ionization of the second OH group of CLA and its disappearance
in the 1H NMR spectra of the complex.
[14] D.K. Roy, A. Saha, A.K. Mukherjee, Spectrochim. Acta A 61 (2005) 2017–2022.
[15] A.M. Slifkin, Charge-Transfer Interaction of Biomolecules, Academic Press, New
York, 1971.
[16] F. Yakuphanoglu, M. Arslan, Solid State Commun. 132 (2004) 229.
[17] S.M. Andrade, S.M.B. Costa, R. Pansu, J. Colloid Interface Sci. 226 (2000) 260.
[18] R. Dabestani, K.J. Reszka, M.E. Sigman, J. Photochem. Photobiol., A 117 (1998)
223.
5. Conclusion
Charge transfer complexation between 2-amino-4-picoline
(2A4P) and chloranilic acid has been studied spectrophotometri-
cally in different polar solvents included acetone, ethanol and ace-
tonitrile. The complex formation was confirmed from the
appearance of a new long wavelength band above 500 nm associ-
ated with color change from colorless to pink. The formation con-
stant has been estimated by using Benesi–Hildebrand equation
where it reached high value confirming high stability of the com-
plex. The high stability of the complex was expected from the high
donation power of the donor due to the presence of two electron
donating groups, the methyl and amino groups. Furthermore, the
formation constant recorded higher values in acetone of lower
electric permittivity compared with ethanol or acetonitrile of high-
er ones. This confirmed the strong interaction between the molec-
ular orbital’s of donor and acceptor in the ground state in less polar
solvent. Some spectroscopic physical parameters like oscillator
strength, transition dipole moment, ionization potential, resonance
energy, charge transfer energy and standard free energy are esti-
mated where they showed solvent dependent. The solid complex
was obtained, its elemental analysis confirmed its formation in
1:1 ratio (donor:acceptor). The infrared spectrum of the solid com-
plex confirmed the presence of proton transfer beside charge
transfer that adds extra stability to it. The measured 1H NMR spec-
tra of the complex in DMSO-d6 confirmed the presence of an equi-
librium between the charge transfer form of the complex and the
hydrogen bonded charge transfer one. Molecular orbital calcula-
tions using GAMESS computations have been applied to predict
and visualizing infrared spectra of reactants and complex. The re-
sults confirmed the presence of charge transfer complex with
hydrogen bonding in agreement with infrared and 1H NMR
measurements.
[19] K. Takahasi, K. Horino, T. Komura, K. Murata, Bull. Chem. Soc. Jpn. 66 (1993)
733.
[20] A. Eychmuller, A.L. Rogach, Pure Appl. Chem. 72 (2000) 179.
[21] K. Brueggermann, R.S. Czernuszewicz, J.K. Kochi, J. Phys. Chem. 96 (1992)
4405.
[22] S.K. Das, G. Krishnamoorthy, S.K. Dofra, Can. J. Chem. 78 (2000) 191.
[23] G. Jones, J.A.C. Jimenez, Tetrahedron Lett. 40 (1999) 8551.
[24] G. Smith, D.E. Lynch, K.A. Byriel, C.H.L. Kennard, J. Chem. Crystallogr. 27 (1997)
307.
[25] G. Smith, D.E. Lynch, R.C. Bott, Aust. J. Chem. 51 (1998) 159.
[26] G. Smith, R.C. Bott, A.D. Rae, A.C. Willis, Aust. J. Chem. 53 (2000) 531.
[27] Z.F R.S. Mulliken, J. Phys. Chem. 56 (1952) 801–822 (Khan, ChemBio3D Ultra
12.0 with GAMESS Interface, the Islamic University, issue: 20.2).
[28] E. Lescrinier, M. Froeyen, P. Herdwin, Nucleic Acids Res. 31 (2003) 2975.
[29] A.S. Al-Attas, M.M. Habeeb, D.S. Al-Raimi, J. Mol. Struct. 928 (2009) 158.
[30] A.S. Al-Attas, M.M. Habeeb, D.S. Al-Raimi, J. Mol. Liq. 148 (2009) 58.
[31] K.M. Al-Ahmary, M.M. Habeeb, E.A. Al-Solmy, J. Sol. Chem. 39 (2010) 1264.
[32] K.M. Al-Ahmary, M.M. Habeeb, E.A. Al-Solmy, J. Mol. Liq. 162 (2011) 129.
[33] K.M. Al-Ahmary, M.M. Habeeb, E.A. Al-Solmy, J. Phys. Chem. Liq. iFirst (2012) 1.
[34] R.M. Alganmi, R.A. Mekheimer, M.M. Habeeb, J. Mol. Liq. 167 (2012) 78.
[35] Y. Iida, Bull. Chem. Soc. Jpn. 43 (1970) 345 (44 (1971) 1777).
[36] J.S. Miller, P.J. Krusics, D.A. Dixon, J. Am. Chem. Soc. 108 (1986) 4459.
[37] L.R. Melby, R.J. Harder, W.R. Hetler, W. Mahler, R.E. Benson, W.E. Mochel, J. Am.
Chem. Soc. 84 (1962) 3374.
[38] M.E. Abdel-Hamid, M. Abdel-Salam, M.S. Mahrous, M.M. Abdel-Khalek, Talanta
32 (1985) 1002.
[39] P. Job, Ann. Chim. Phys. 9 (1928) 113.
[40] D.A. Skoog, Principal of Instrumental Analysis, third ed., Sunder College
Publisher, New York, 1985.
[41] H.A. Benesi, J.H. Hildebrand, J. Am. Chem. Soc. 71 (1949) 2703.
[42] A. Airinei, M. Homocianu, D.O. Dorohol, J. Mol. Liq. 157 (2010) 13.
[43] A.B.P. Leve, Inorganic Electro Spectros, second ed., Elsevier, Amsterdam, 1985.
[44] E.M. Voigt, C. Reid, J. Am. Chem. Soc. 86 (1964) 3930.
[45] R. Rathore, S.V. Linderman, J.K. Kochi, J. Am. Chem. Soc. 119 (1997) 9393.
[46] W.B. Person, J. Am. Chem. Soc. 84 (1962) 536.
[47] H.M. McConnel, J.J. Ham, J.R. Platt, J. Chem. Phys. 21 (1953) 66.
[48] G. Briegleb, Angew. Chem. 76 (1964) 326.
[49] D.C. Wheat, Hand Book of Chemistry and Physics, 15th ed., CRC, 1969.
[50] F.A. Masten, J. Chem. Phys. 24 (1956) 602.
[51] Y.S. El-Sayed, Spectrochim. Acta A 78 (2011) 1227.
[52] G. Briegleb, J. Czekalla, Z. Physik Chem. (Frankfurt) 24 (1960) 37.
[53] A.E. Mourad, Spectrochim. Acta A 41 (1985) 347.
[54] M. Pandeeswaran, K.P. Elango, Spectrochim. Acta A 65 (2006) 1148.
[55] M.H. Irving, T.S. Freiser, West. IUPAC compendium of analytical nomenclature
definitive rules, Pergamum Press, Oxford, 1981.
References
[1] M.K. Das, P.K. Maiti, S. Roy, M. Mittakanli, K.W. Morse, I.H. Hall, Arch. Pharm.
(Weinheim) 325 (1992) 267–272.