Spectrophotometric, Thermodynamic and Density Functional Studies of Charge Transfer Complex Between Benzhydryl Piperazine and 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone

Abstract

The charge transfer complex of benzhydryl piperazine as donor with the π-acceptor 2,3-dichloro-5,6-dicyano-p-benzoquinone has been studied spectrophotometrically in acetonitrile medium at different temperatures. On mixing the donor with acceptor, a reddish brown colored charge transfer complex is formed. Electronic absorption spectra of the complex show charge transfer bands at 587, 546 and 457 nm. The molecular composition of the complex was studied by applying Job’s continuous variation and spectrophotometric titration methods. These results support the formation of the complex in a 1:2 ratio. The Benesi–Hildebrand equation has been applied to compute the formation constant and molecular extinction coefficient. Thermodynamic parameters of the charge transfer complexation reaction (standard entropy, standard enthalpy and standard Gibbs free energy) have been calculated. The results of the spectrophotometric study demonstrated that the charge transfer complex formation is endothermic. The computational studies of the charge transfer complex were performed by using the Gaussian 09 W package of programs. The bond lengths, bond angles, dihedral angles, Mulliken atomic charges, molecular electrostatic potential maps and characterization of the highest occupied molecular orbital and lowest unoccupied molecular orbital surfaces of charge transfer complex were computed.