Asok K. Mukherjee

Charge-transfer complex formation between o-chloranil and a series of polynuclear aromatic hydrocarbons.

The equilibrium constants, enthalpies and entropies of formation of molecular electron donor-acceptor (EDA) complexes of o-chloranil with a series of aromatic hydrocarbons have been determined spectrophotometrically. Spectroscopic and thermodynamic aspects of these complexes have been analysed.

Room temperature solution studies of complexation between o-chloranil and a series of anilines by spectrophotometric method.

Electron donor-acceptor (EDA) complex formation between o-chloranil and a series of anilines has been studied in CCl4 medium. In all the cases, EDA complexes are formed instantaneously on mixing the donor and acceptor solutions. N,N-dimethylaniline and N,N-dimethyl-p-toluidine form stable EDA complexes with o-chloranil while the other complexes decay slowly into secondary products. The kinetics of all these reactions has been studied by UV-VIS absorption spectrophotometric method and the rate constants of the reactions and formation constants of the EDA complexes have been determined. The charge transfer (CT) transition energies of the complexes are found to change systematically with change in the number and position of the methyl groups in the donor molecules (methylanilines). From an analysis of this variation, the electron affinity of o-chloranil has been found to be 2.54 eV. A perturbational inductive effect Hückel parameter hMe has been found from this trend and the value obtained (-0.27) is very close to that (-0.3) obtained by Lepley (J. Am. Chem. Soc., 86 (1964) 2545) from a study of tetracyano ethylene (TCNE)-methylbenzene complexes.

Study of the formation equilibria of electron donor-acceptor complexes between [60]fullerene and methylbenzenes by absorption spectrometric method.

The electron donor-acceptor (EDA) interaction between [60]fullerene and three methylbenzenes, viz., durene, pentamethylbenzene and hexamethylbenzene has been studied in carbon tetrachloride medium at a number of temperatures. It has been found that these methylbenzenes form stable 1:1 EDA complexes with [60]fullerene. Charge transfer (CT) absorption bands of the complexes in the 410-460 nm region are more intense than the usual 420-700 nm absorption band of C60. The CT transition energies (hvCT) of the complexes change systematically with change in the number and position of the methyl groups in the donor molecules (methylbenzenes) and also with the donor ionisation potentials. From an analysis of this variation the electron affinity of C60 has been found to be 2.30 eV and also an inductive effect Hückel parameter of the methyl group has been determined. Formation constants (K) have been determined at three different temperatures from which the enthalpies and entropies of formation of the complexes have been determined.

Study of ground state EDA complex formation between [70]fullerene and a series of polynuclear aromatic hydrocarbons

[70]fullerene has been shown to form 1:1 EDA complex with anthracene, naphthalene, phenanthrene, pyrene and acenaphthene in CCl4 medium. Charge transfer (CT) bands have been detected in all the cases. Isosbestic points have been observed in the cases of phenanthrene and acenaphthene complexes. Ionisation potentials of the donors and CT transition energies have been found to correlate in accordance with Mulliken equation and from this correlation the electron affinity of C70 has been found to be 2.59 eV. Enthalpies and entropies of formation of the complexes have been estimated from the formation constants of the complexes determined spectrophotometrically at three different temperatures.

Absorption spectroscopic study of EDA complexes of [70] fullerene with a series of methyl benzenes

[70]Fullerene has been shown to form 1:1 molecular complexes with toluene, p-xylene, m-xylene, 1,2,4,5-tetramethyl benzene (durene) and pentamethyl benzene (PMB) in CCl4 medium by absorption spectroscopic method. Isosbestic points have been detected in case of complexes with PMB and durene. Charge transfer absorption band could not be detected but the intensity of the broad absorption band of C70 in CCl4 decreases systematically with increase in the concentration of the added methylbenzenes. From this trend the formation constants (Kc) of the complexes have been determined at three different wavelengths. The constancy of Kc with respect to change in the wavelength of measurement supports the view that complex of a single stoichiometry (1:1) is formed in each case.

Ground state EDA complex formation between [60]fullerene and a series of polynuclear aromatic hydrocarbons

Formation constants of 1∶1 adducts of [60]fullerene with naphthalene, phenanthrene, anthracene, pyrene and chrysene have been determined in CCl4 medium. Ionisation potentials of donor molecules and charge transfer (CT) transition energies of the [60]fullerene adducts have been found to correlate in accordance with the Mulliken equation. From such correlation the electron affinity of [60]fullerene has been calculated to be 2.32 eV in solution. A good estimate for the sp2C–sp2C resonance integral β in benzenoid hydrocarbons has also been obtained from the observed CT transition energies.

Spectrophotometric study of molecular complex formation between o-chloranil and a series of methylated pyridines

o-Chloranil has been shown to form 1:1 molecular complexes with pyridine and 2-, 3- and 4-picolines in CCl4 medium. Isosbestic points have been found but charge-transfer bands could not be detected. The formation constants of the complexes exhibit a very good linear free energy relationship from which the Hammett p parameter for the complexation reaction is found to be -3.67.

A PASCAL'S TRIANGLE-LIKE APPROACH FOR THE DETERMINATION OF CHARACTERISTIC POLYNOMIAL COEFFICIENTS OF RECIPROCAL GRAPHS

Characteristic polynomial coefficients of three classes of graph, namely Ln + n(p), Cn + n(p) and K 1,n-1 + n(p), which are known to have reciprocal pairs of eigenvalues, have been shown to be generated by simple manipulation of the Pascals triangle.

Inclusion of riboflavin in β-cyclodextrin: A fluorimetric and absorption spectrometric study

Formation of inclusion complexes between riboflavin and beta-cyclodextrin (beta-CD) with both 1:1 and 1:2 stoichiometry has been established by fluorimetric titration. However, in absorption spectrometric experiment, spectral change of riboflavin in the visible range could be observed only by taking beta-CD at a much higher concentration (about 100 times) than riboflavin and under such condition only 1:2 complexes could be detected. Its formation constant (K) was determined by a multiple linear regression analysis of the absorption data. The reliability of the K value was confirmed by the consistency achieved on analyzing the data at two different wavelengths.

Absorption spectrometric study of molecular complex formation between [60]fullerene and a series of methylated pyridines

[60]fullerene has been shown to form 1:1 molecular complexes with pyridine and some methylated pyridines such as 2-picoline, 3-picoline, 4-picoline, 2,6-lutidine and 2,4,6-collidine in CCl4 medium by absorption spectrometric method. Well defined charge transfer (CT) bands have been observed for complexes of C60 with all the pyridines studied except 4-picoline. From an analysis of the trends in the CT absorption bands the ionisation potentials of the methylpyridines have been determined. The electron affinity of C60 has also been determined from the spectral data. The formation constants of the complexes exhibit a very good linear free energy relationship from which the Hammett p parameter for the complexation process is found to be -2.96.