Systematic measurements of charge transfer complexes caused from 1-phenyl-1,2,3,4-tetrahydroisoquinoline and 4-aminoacetanilide with series of π-acceptors (BQ, DDQ, TCNQ).

Molecular charge-transfer interaction of a series of electron π-acceptors of 1,4-benzoquinone (BQ), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and Tetracyanoquinodimethane (TCNQ) with selected donors of 1-phenyl-1,2,3,4-tetrahydroisoquinoline (PTHIQ) and 4-aminoacetanilide (ACE) have been studied in methanol at room temperature. The stoichiometry of the complexes was determined by photometric titration method and was found to be 1:1, in all the cases. Spectro-kinetic interaction studies along with rate constants and observed formation constants (K) indicated that the strength of the complex formations is PTHIQ-BQ < PTHIQ-DDQ < PTHIQ-TCNQ. Also, Similar observations happened in ACE-BQ and < ACE-DDQ < ACE-TCNQ systems. FT-IR results indicated that the point of interaction was identifying in NH moiety of PTHIQ and NH2 moiety of ACE with series of π-acceptor complexes. The experimental results were compared with Ab initio DFT calculations at the B3LYP/6-31 + G(d) level of theory. The increasing order of the experimentally measured formation constant of CT-complexes (PTHIQ and ACE with series of acceptors) was well supported by theoretical HOMO-LUMO energy gap and drastically changes in Mulliken charges of NH moiety of PTHIQ, NH2 moiety of ACE with complexation with acceptors.

Molecular complexes of l-phenylalanine with substituted 1,4-benzoquinones in aqueous medium: spectral and theoretical investigations.

Various spectral techniques such as UV-Vis, FT-IR, and fluorescence have been employed to investigate the charge transfer interaction of L-phenylalanine (LPA) with substituted 1,4-benzoquinones (MQ(1-4)). Kinetic and thermodynamic properties of the complexes were determined in aqueous medium at physiological condition (pH=7). The interaction of MQ(1-4) with L-phenylalanine (LPA) was found to proceed through the formation of donor-acceptor complex, yielding a radical anion. The stoichiometry of the complexes was determined by Jobs continuous variation method and was found to be 1:1 in all the cases. Fluorescence quenching studies showed that the interaction between the donor and the acceptors is spontaneous. The results indicated that the progressive replacement of chlorine atom (-I effect) by methoxy group (+M effect) in the quinone decreased the electron acceptor property of the quinone. The order of the experimentally measured association constant of these complexes was well supported by DFT/B3LYP calculations.

Charge transfer complexes of quinones in aqueous medium: spectroscopic and theoretical studies on interaction of cimetidine with novel substituted 1,4-benzoquinones and its application in colorimetric sensing of anions.

For the first time, the charge transfer (CT) complexes of quinones in aqueous medium have been reported. A series of novel water soluble 1,4-benzoquinones possessing variable number of chloro and methoxy substituents has been employed as electron acceptors (MQ1-4) in the CT complexation with cimetidine (CTD) drug. The mechanism of the interaction has been investigated using various spectral techniques such as UV-Vis, (1)H NMR and FT-IR spectra. The rate of the CT interaction was observed to decrease with progressive replacement of chloro by methoxy substituent in the quinone and this variation is well supported by the formation constant and enthalpy of activation values. Ab initio DFT calculations predicted that the variation in the bond lengths of the carbonyl moieties and the charge densities on the carbonyl oxygen atoms depend largely on the nature of the substituent present in the quinone ring. Also, the HOMO(Donor)-LUMO(Acceptor) energy gaps correlate linearly with the formation constants of the CT complex. The equilibrium, kinetic, electrochemical and theoretical investigations of the CT interaction of these quinones indicated that progressive replacement of electron withdrawing chlorine atom (-I effect) by an electron releasing methoxy group (+M effect) makes these acceptors progressively weaker. The charge-transfer complex, formed between CTD and monomethoxy quinone derivative, has been employed as a new class of chromogenic sensor for the colorimetric sensing of fluoride and acetate ions.

Substituent effect on the electron acceptor property of 1,4-benzoquinone towards the formation of molecular complex with sulfamethoxazole.

UV-Vis, (1)H NMR, FT-IR, LC-MS and fluorescence spectral techniques were employed to investigate the mechanism of interaction of sulfamethoxazole with varying number of methoxy/chloro substituted 1,4-benzoquinones (MQ1-4) and to characterize the reaction products. The interactions of MQ1-4 with sulfamethoxazole (SULF) were found to proceed through the formation of a donor-acceptor complex, containing radical anion and its conversion to the product. Fluorescence quenching studies showed that the interaction between the donor and the acceptors are spontaneous. The results indicated that the progressive replacement of chlorine atom (-I effect) by methoxy group (+M effect) in the quinone decreased the electron acceptor property of the quinone. The results of the correlation of experimentally measured binding constants with electrochemical data and ab initio DFT calculations supported these observations.

Spectroscopic investigation on the mechanism of formation of molecular complexes of albendazole and trimethoprim with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone.

UV-vis, (1)H NMR, FT-IR, mass and fluorescence spectral techniques were employed to investigate the mechanism of interaction of albendazole and trimethoprim with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and to characterize the reaction products. The interaction of DDQ with trimethoprim (TMP) and albenadazole (ALB) were found to proceed through the formation of donor-acceptor complex, containing DDQ radical anion and its conversion to the product. Fluorescence quenching studies indicated that the interaction between the donors and the acceptor are spontaneous and the interaction of TMP-DDQ (binding constant=2.9×10(5)) is found to be stronger than that the ALB-DDQ (binding constant=3×10(3)) system. Also, the binding constant increased with an increase in polarity of the medium indicating the involvement of radical anion as intermediate.

Molecular complexes of ketaconazole and oxatomide with p-chloranil: spectroscopic and spectrofluorimetric studies.

The molecular complexes of the donors ketaconazole (KTZ) and oxatomide (OXA) drugs with 2,3,5,6-tetrachloro-1,4-benzoquinone (p-chloranil, p-CHL) have been investigated spectroscopically (UV-vis, FT-IR and 1H NMR) and spectrofluorimetrically in different solvents and temperatures. The stoichiometry of the complexes was found to be 1:1. The data are discussed in terms of formation constant, molar extinction coefficient, oscillator strength, dipole moment, ionization potential, dissociation energy and thermodynamic parameters. The results indicated that the formation of molecular complex is spontaneous and endothermic. The fluorescence quenching studies indicated that the interaction of the donors is spontaneous and the fluorescence quenching increased with an increase in the intensity of complexation with the acceptor.

Spectroscopic and spectrofluorimetric studies on the interaction of irbesartan with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and iodine.

Raman, UV-vis, 1H NMR, FT-IR, mass and fluorescence spectral techniques were employed to investigate the mechanism of interaction of irbesartan (IRB) drug with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and iodine. Interaction of IRB with iodine yields triiodide ion and its formation was confirmed by electronic and Raman spectra. The peaks appeared in Raman spectrum of the isolated product at 143, 113 and 76 cm(-1) are assigned to νas(I-I), νs(I-I) and δ(I3-) respectively, confirmed the presence of I3- ion. The interaction of DDQ with irbesartan was found to proceed through the formation of outer complex and its conversion to the CT complex. Formation constant (K), molar extinction coefficient (ɛ) and thermodynamic properties ΔH#, ΔS# and ΔG# were determined and discussed. Fluorescence quenching studies indicated that the interaction between the IRB and the acceptors are spontaneous and the IRB-DDQ interaction is found to be stronger than that the other system. Solvent variation studies indicated that the binding constant increased with an increase in polarity of the medium.