Diffusion-ordered spectroscopy (DOSY) is a powerful and efficient technique for the analysis of complex mixtures, relying on their differential in self-diffusion coefficient. However, DOSY is often struggled to separate signals pertaining to isomeric species, especially positional isomers. Here, for the first time, we describe the novel design of 18-crown ether-6 (18C6) and 18C6/K⁺ complex as matrixes to discriminate and identify positional isomeric mixtures of phenylenediamine, nitroaniline, phthalic acid, dimethoxybenzoic acid, aminophthalic acid and even amino acids using ¹H DOSY spectrum. The superior performance of 18C6 and 18C6/K⁺ complex as matrix depends on that they can interact with different components with varying binding energy as demonstrated by MMMF calculations and the DFT calculation. The methodology presented here is simple yet efficient. Moreover, the crown ether and crown ether/K⁺ complex provide the dual mode discrimination for both amino and carboxylic substituted positional isomers.

扩散有序光谱 (DOSY) 是一种强大而有效的分析复杂混合物的技术，依赖于它们在自扩散系数方面的差异。然而，DOSY 经常难以分离与异构物种有关的信号，尤其是位置异构体。在这里，我们首次描述了 18-冠醚-6 (18C6) 和 18C6/K ⁺复合物作为基质的新设计，以区分和识别苯二胺、硝基苯胺、邻苯二甲酸、二甲氧基苯甲酸、氨基邻苯二甲酸的位置异构混合物甚至氨基酸使用¹ H DOSY 谱。18C6和18C6/K ⁺的优越性能复杂的矩阵取决于它们可以与具有不同结合能的不同组分相互作用，如 MMMF 计算和 DFT 计算所示。这里介绍的方法简单而有效。此外，冠醚和冠醚/K ⁺复合物为氨基和羧基取代的位置异构体提供了双重模式区分。