Synthesis and spectroscopic studies on charge-transfer molecular complexes formed in the reaction of imidazole and 1-benzylimidazole with σ- and π-acceptors.

Aaron J Clark, Michael Safaee, Taemin Oh, Michael E Ivan, Vamsi Parimi, Rintaro Hashizume, Tomoko Ozawa, Charles D James, Orin Bloch, Andrew T Parsa

Index: Spectrochim. Acta. A. Mol. Biomol. Spectrosc. 79(5) , 1613-20, (2011)

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Abstract

The spectrophotometric characteristics of the solid charge-transfer molecular complexes (CT) formed in the reaction of the electron donors imidazole (IML) and 1-benzylimidazole (BIML) with the σ-acceptor iodine and π-acceptors 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), tetracyanoethylene (TCNE) and 2,3,5,6-tetrachloro-1,4-benzoquinone (CHL) have been studied in chloroform at 25 °C. These were investigated through electronic and infrared spectra as well as elemental analysis. The results show that the formed solid CT-complexes have the formulas [(IML)2 I]I3, [(IML)(DDQ)], [(IML)2(TCNE)5] and [(IML)(CHL)] for imidazole and [(BIML) I]I3, [(BIML)(DDQ)2], [(BIML)(TCNE)2] and [(BIML)(CHL)2] for 1-benzylimidazole in full agreement with the known reaction stoichiometries in solution as well as the elemental measurements. The formation constant KCT, molar extinction coefficient ɛCT, free energy change ΔG0, CT energy ECT and ionization potential Ip have been calculated for the CT-complexes [(IML)2 I]I3, [(IML)(DDQ)], [(IML)(CHL)], [(BIML) I]I3, [(BIML)(DDQ)2], [(BIML)(TCNE)2] and [(BIML)(CHL)2].Copyright © 2011 Elsevier B.V. All rights reserved.