Crown ether and crown ether/K+ complex assisted DOSY NMR: A versatile tool for positional isomers identification in aqueous solution

Abstract 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.