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1,2 - 二甲基咪唑作为电子供体与π受体2,4 - 二硝基 - 1 - 萘酚在不同极性溶剂中电荷转移配合物的合成及光谱研究

Synthesis, and spectroscopic studies of charge transfer complex of 1,2-dimethylimidazole as an electron donor with π-acceptor 2,4-dinitro-1-naphthol in different polar solvents.

作者信息

Miyan Lal, Khan Ishaat M, Ahmad Afaq

机构信息

Department of Chemistry, Faculty of Science, Aligarh Muslim University, Aligarh 202002, UP, India.

Department of Chemistry, Faculty of Science, Aligarh Muslim University, Aligarh 202002, UP, India.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2015 Jul 5;146:240-8. doi: 10.1016/j.saa.2015.02.060. Epub 2015 Feb 21.

Abstract

The charge transfer (CT) complex of 1,2-dimethylimidazole (DMI) as an electron donor with π acceptor 2,4-dinitro-1-naphthol (DNN) has been studied spectrophotometrically in different solvents like chloroform, acetonitrile, methanol, methylene chloride, etc. at room temperature. The CT complex which is formed through the transfer of lone pair electrons from DMI to DNN exhibits well resolved CT bands and the regions of these bands were remarkably different from those of the donor and acceptor. The stoichiometry of the CT complex was found to be 1:1 by a straight-line method between donor and acceptor with maximum absorption bands. The novel CT complex has been characterized by FTIR, TGA-DTA, powder XRD, (1)H NMR and (13)C NMR spectroscopic techniques. The Benesi-Hildebrand equation has been used to determine the formation constant (K(CT)), molar extinction coefficient (ε(CT)), standard gibbs free energy (ΔG°) and other physical parameters of the CT complex. The formation constant recorded higher values and molar extinction coefficient recorded lower values in chloroform compared with methylene chloride, methanol and acetonitrile, confirming the strong interaction between the molecular orbital's of donor and acceptor in the ground state in less polar solvent. This CT complex has been studied by absorption spectra of donor 1,2-dimethylimidazole (DMI) and acceptor 2,4-dinitro-1-naphthol (DNN) by using the spectrophotometric technique in various solvents at room temperature.

摘要

以1,2 - 二甲基咪唑(DMI)作为电子供体与π受体2,4 - 二硝基 - 1 - 萘酚(DNN)形成的电荷转移(CT)配合物,已在室温下于氯仿、乙腈、甲醇、二氯甲烷等不同溶剂中通过分光光度法进行了研究。通过孤对电子从DMI转移至DNN形成的CT配合物呈现出分辨率良好的CT带,且这些带的区域与供体和受体的区域明显不同。通过供体和受体之间具有最大吸收带的直线法发现CT配合物的化学计量比为1:1。该新型CT配合物已通过傅里叶变换红外光谱(FTIR)、热重 - 差热分析(TGA - DTA)、粉末X射线衍射(XRD)、核磁共振氢谱(¹H NMR)和核磁共振碳谱(¹³C NMR)光谱技术进行了表征。使用贝内西 - 希尔德布兰德方程来确定CT配合物的形成常数(K(CT))、摩尔消光系数(ε(CT))、标准吉布斯自由能(ΔG°)及其他物理参数。与二氯甲烷、甲醇和乙腈相比,氯仿中记录的形成常数更高,摩尔消光系数更低,这证实了在极性较小的溶剂中基态下供体和受体分子轨道之间的强相互作用。在室温下,通过分光光度技术利用供体1,2 - 二甲基咪唑(DMI)和受体2,4 - 二硝基 - 1 - 萘酚(DNN)的吸收光谱对该CT配合物进行了研究。

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