The absorption maxima and equilibrium constants of quinone-aromatic complexes have been determined spectrophotometrically. The charge-transfer transition energy is found to obey a linear relationship with ionization energy of hydrocarbons and aza-hydrocarbons. The equilibrium constants increase with decrease of ionization potential.

M CHOWDHURY

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Charge-transfer interaction between quinone and aromatics

Transactions of the Faraday Society

The molecular charge-transfer absorption bands have been detected in mixtures of tetrahalo p-benzoquinones and polynuclear aromatic hydrocarbons in chloroform, carbon tetrachloride and methyl acetate solutions. The plot of charge-transfer interaction energies against ionization energies of hydrocarbons was found to be linear. For the isolated complexes, the charge transfer interaction was found to be in the order hv(iodanil)>hv (bromanil)>hv (chloranil) for all hydrocarbons, although in solution the order was anomalous. For the complexes of the same donor with different acceptors the oscillator strength of the charge-transfer absorption band was found to increase with an increase in equilibrium constant. No such correlation was noticed with complexes of different donors with the same acceptor. The equilibrium constant increased with the lowering of the ionization energy of the hydrocarbon. There was nearly a hundredfold increase in dipole moment of the complexes on electronic excitation. The evaluation of Mulliken's a and b coefficients showed that the charge transfer-complexes of tetrahalo p-benzoquinones with polynuclear aromatic hydrocarbons are weak complexes. © The Faraday Society and Contributors, 1964.

Charge transfer interaction between tetrahalo p-benzoquinones and polynuclear aromatic hydrocarbons

The charge transfer interaction energy against π-ionization energy plot for tetrachloro phthalic anhydride and a number of aromatic hydrocarbon and azahydrocarbon systems has been found to be linear with unit slope. The equilibrium constant for the charge transfer complexes has been found to increase with the lowering of the ionization energy of the donor, but the molar extinction coefficient-equilibrium constant relation was anomalous.

Charge transfer interaction between tetrachloro phthalic anhydride and aromatics

The characteristic charge-transfer absorption frequencies of a number of I2-hydrocarbon complexes in carbon tetrachloride solution have been found to follow the relation hv = ID - EA - Δ, and the stabilization energy Δ was constant for the whole series and was equal to 3.256 eV. Except the calculated values of molar extinction coefficients of the complexes, most of the experimental results appeared to support the general conclusion derived from Mulliken's theory of intermolecular charge transfer interaction. The experimental data, however, suggest that the extinction coefficients may not be dependent on the nature of the hydrocarbon part of the complex.

Journal	Transactions of the Faraday Society
Publisher	-
ISSN	0014-7672