冠醚与金属离子络合的热力学研究进展

F. Nasri
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摘要

近年来,大环和超分子化学已成为化学、物理和生物相互作用的一个有希望的研究领域。杜邦的Charles J. Pedersen在20世纪60年代早期发现了一种化合物,后来以二苯并-18-冠-6 (DB18C6)而闻名。溶液中络合物的检测,结果络合物的稳定性的指定,以及络合物的热力学或动力学参数的确定可以通过多种物理化学测量来实现。大环的构象刚性或柔韧性对其选择性行为有相当大的影响。大环上给体原子的数目、类型和排列对大环选择性起主要作用。根据化学术语,这被称为“主-客”化学,其中醚扮演宿主的角色,离子作为客体。在有机溶液中,冠醚起到相转移催化剂和助剂的作用,以提高无机盐的溶解性。在络合过程中,大环需要与溶剂分子争夺阳离子。因此,溶剂的变化使这些配体的明显结合特性发生了相当大的变化。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
A Review of the Thermodynamics of Complexation of Crown Ethers With Metal Ion
Recently, macrocyclic and supramolecular chemistry has reached a hopeful area of research in the mutual interaction between chemistry, physics and biology. Charles J. Pedersen, at du Pont figure out a compound in the early 1960s famous for dibenzo-18-crown-6 (DB18C6) later on. The detection of the complex formation in solution, the designation of the stability of the consequence complex or complexes and the determination of the thermodynamic or the kinetic parameters of the complex formation can be attained by a manifold of physicochemical measurements. Conformational rigidity or flexibility of macrocycles has a considerable penetration on their selective behavior. The number, type, and arrangement of donor atoms in the macrocyclic rings play a main role in macrocycle selectivity. Based on chemistry terminology, this is known as “host-guest” chemistry where the ether plays the role as the host and the ionic species as the guest. In organic solutions, crown ethers take the role of phase-transfer catalysts and agents in order to enhance the solubility of inorganic salts. Macrocycles need to compete with solvent molecules for the cations during the process of complexation. Consequently, variation of the solvent makes a considerable change in the manifest binding characteristics of these ligands.
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