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Comparison of the Electrochemical Properties of Two Structurally Different Novel bis-Schiff Bases

机译:两种结构不同的新型双席夫碱的电化学性质比较

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Two novel symmetrical bis-Schiff bases ((1E)-1-N-{[4-(4-{[(E)-N-(2-aminophenyl) carboxyimidoyl]phenoxy} butoxy) phenyl]methylidene}benzene-1,2-diamine (compound 1) and (1E)-1-N-{[4-(4- {[(E)-N-(4-aminophenyl) carboxyimidoyl] phenoxy} butoxy) phenyl]methylidene}benzene-1,4- diamine (compound 2) were synthesized and characterized by means of single-crystal X-ray diffraction(1), FT-IR and NMR spectroscopy (1,2), elemental (1,2), TG/DSC and electrochemical analysis (1,2).The prepared compounds are positional isomers that display very different electrochemical behaviour.Electrochemical study has shown that the oxidation of the investigated Schiff base (1) is irreversible,diffusion controlled process, and that the oxidation products are adsorbed on the glassy carbonelectrode surface. Oxidation of a Schiff base (2) is reversible (follows EC reaction mechanism),diffusion controlled, and the oxidation products are also adsorbed on the glassy carbon electrodesurface. Considering molecular structure of compounds, molecule 1 is planar, with small deviation ofatoms from the calculated plane. The planarity of molecule 1 is stabilized by untypical intramolecularinteraction of amino and imino nitrogen atoms. In the crystal, the molecules are primarily linked byhydrogen bonds involving primary amino groups and weak C-H interactions. Consequently, theseinteractions are arranging molecules into herringbone packing motif. Crystal structure of molecule 2could not be determined but it is predicted based upon similarity with molecule 1 and interpretation ofthe spectral data (NMR and FTIR).
机译:两个新颖的对称双席夫碱((1E)-1-N-{[4-(4-{[(E)-N-(2-氨基苯基)羧酰亚胺基]苯氧基}丁氧基)苯基]亚甲基}苯-1, 2-二胺(化合物1)和(1E)-1-N-{[4-(4-{[((E)-N-(4-氨基苯基)羧酰亚胺基]苯氧基}丁氧基)苯基]亚甲基}苯-1,合成4-二胺(化合物2)并通过单晶X射线衍射(1),FT-IR和NMR光谱(1,2),元素(1,2),TG / DSC和电化学分析进行表征(1,2)。制备的化合物为位置异构体,表现出非常不同的电化学行为。电化学研究表明,研究的席夫碱(1)的氧化是不可逆的,扩散控制过程,并且氧化产物被吸附在席夫碱(2)的氧化是可逆的(遵循EC反应机理),扩散受控,并且氧化产物也吸附在玻碳电极表面。化合物1的分子是平面的,与计算平面的原子偏差很小。分子1的平面性通过氨基和亚氨基氮原子的非典型分子内相互作用而稳定。在晶体中,分子主要通过氢键连接,该氢键涉及伯氨基和弱的C-H相互作用。因此,这些相互作用将分子排列成人字形的填充图案。分子2的晶体结构无法确定,但可以根据与分子1的相似性以及对光谱数据(NMR和FTIR)的解释进行预测。

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