Spectroscopic characterization of hydrogen-bonded proton transfer complex between 4-aminopyridine with 2,6-dichloro-4-nitrophenol in different solvents and solid state

Proton transfer reaction between the proton donor 2,6-dichloro-4-nitrophenol (DCNP) with the proton acceptor 4-aminopyridine (4APy) has been investigated spectrophotometrically in different solvents included the aprotic solvent acetonitrile (MeCN), the protic one methanol (Me0H) and a mixture consists of 50% acetonitrile + 50% dichloroethane (ANDC). The proton transfer complex is produced instantaneously with deep yellow color and absorption maxima in the range 395-425 nm. The composition of the complex was characterized spectrophotometrically to be 1:1 in all solvent proving that the solvent has no effect on the complex stoichiometry. The proton transfer formation constant has been estimated by using Benesi-Hildebrand equation where the highest value was recorded in the mixture ANDC. This proofs the high stability of the complex in less polar solvent as a result of the high stability of the complex ground state. The solid complex has been synthesized and characterized by elemental analysis to be 1:2 [(proton donor) (proton acceptor)(2)]. The obtained solid complex was analyzed by infrared spectroscopy where two broad band's at 3436 and 2500 cm(-1) characterized for asymmetric NHN hydrogen bond were identified. Molecular modeling utilizing GAMESS computations as a package of ChemBio3D Ultral2 program was carried out where asymmetric NHN+ was explored with NN bond distance 2.77 angstrom. The computations showed a difference in molecular geometry of the complex compared with reactants especially bond lengths, bond angles and distances of close contact. (C) 2014 Elsevier B.V. All rights reserved.