Abstract
Electron donor–acceptor molecular complexes of a few phenolic donors with some quinonoid and tetracyanoethylene acceptors have been prepared by two different methods, i.e., by simple grinding of the respective component pair in the solid-state and in solution. Both the methods yielded identical dark colored 1:1 stoichiometric complexes. Spectral studies revealed that the complexes are ionic in nature. The g values obtained in ESR spectral studies for all these molecular adducts vary between 2.000 and 2.022, confirming the free radical nature of the adducts. The electronic absorption spectral studies proved that the donor–acceptor complexes formed initially, exhibit new electronic transitions at longer wavelengths, are less stable and disassociate readily into ionic type of adducts. The absorption maximum at longer wavelengths, i.e. ≥550 nm, are assigned to the charge transfer complexes, while the new transition at around 410 ± 5 nm is attributed to the anion radical of the adducts. The ease of complexation not only depends on the ionization potential and electron affinities of the phenolic donors and the acceptors but is also structure sensitive. Complexation is confirmed by the shift in IR absorption of the phenolic hydroxyl group and the carbonyl group of quinone acceptors and the cyano group of tetracyanoethylene. Proton magnetic resonance studies indicate an interaction between the phenolic donors and acceptors on basis of the altered chemical shifts. Further, IR and NMR studies show that the stability of the adducts is governed not only by the charge transfer interaction but also by hydrogen bonding.
Published Version
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More From: Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
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