Studies on the weak interactions and CT complex formations between chloranilic acid, 2,3-dichloro-5,6-dicyano-p-benzoquinone, tetracyanoethylene and papaverine in acetonitrile and their thermodynamic properties, theoretically, spectrophotometrically aided by FTIR

Spectrophotometric, FTIR and theoretical studies of the charge-transfer complexes between mild narcotic drug papaverine and the acceptors chloranilic acid (Cl-A), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) and tetracyanoethylene (TCNE) in acetonitrile, their association constants, thermodynamic (ΔG(0), ΔH(0) and ΔS(0)) and other related properties had been described. Papaverine was found to form colored charge-transfer complexes with Cl-A, DDQ and TCNE in acetonitrile. The absorption maxima of the complexes were 518.5, 584.0 and 464.0 nm for Cl-A complex, DDQ complex, and TCNE complex respectively. The compositions of the papaverine complexes were determined to be 1:1 from Job's method of continuous variation. Solid complexes formed between papaverine and the acceptors were isolated. Comparison of the FTIR spectra of the solid complexes between papaverine and the acceptors and their constituents showed considerable shift in absorption peaks, changes in intensities of the peaks and formation of the new bands on complexation. However, no attempt has been made to purify the complexes and study the detailed spectra both theoretically and experimentally. The energies hν(CT) of the charge-transfer complexes were compared with the theoretical values of hν(CT) of the complexes obtained from HOMO and LUMO of the donor and the acceptors. The reasons for the differences in hνCT values were explained. Density function theory was used for calculation. hν(CT) (experimental) values of the transition energies of the complexes in acetonitrile differed from hν(CT) (theoretical) values. ID(V) value of papaverine was calculated. Charge-transfer complexes were assumed to be partial electrovalent compounds with organic dative ions D(+) and A(-) (in the excited state) and attempts had been made to correlate the energy changes for the formation of the complexes with the energy changes for the formation of electrovalent compounds between M(+) and X(-) ions.