Department of Chemistry, Texas A&M University at Qatar, P.O. Box 23874, Doha, Qatar.
Spectrochim Acta A Mol Biomol Spectrosc. 2011 Sep;79(5):1613-20. doi: 10.1016/j.saa.2011.05.021. Epub 2011 Jun 7.
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].
在 25°C 的氯仿中研究了电子给体咪唑 (IML) 和 1-苄基咪唑 (BIML) 与 σ-受体碘以及 π-受体 2,3-二氯-5,6-二氰基-1,4-苯醌 (DDQ)、四氰乙烯 (TCNE) 和 2,3,5,6-四氯-1,4-苯醌 (CHL) 反应形成的固体质子转移分子配合物 (CT) 的分光光度特性。这些通过电子和红外光谱以及元素分析进行了研究。结果表明，形成的固态 CT 配合物具有化学式 [(IML)2 I]I3、[(IML)(DDQ)]、[(IML)2(TCNE)5] 和 [(IML)(CHL)] 对于咪唑和 [(BIML) I]I3、[(BIML)(DDQ)2]、[(BIML)(TCNE)2] 和 [(BIML)(CHL)2] 对于 1-苄基咪唑，完全符合溶液中已知的反应化学计量以及元素测量。对于 CT 配合物 [(IML)2 I]I3、[(IML)(DDQ)]、[(IML)(CHL)]、[(BIML) I]I3、[(BIML)(DDQ)2]、[(BIML)(TCNE)2] 和 [(BIML)(CHL)2]，计算了形成常数 KCT、摩尔消光系数 ɛCT、自由能变化 ΔG0、CT 能量 ECT 和电离势 Ip。
