Recognition of carboxylic acids and phosphonic acids using a 1,8-diphenylanthracene-based diguanidine in solution and solid states

Abstract

A 1,8-diphenylanthracene-based diguanidine 1 has been designed and synthesized for the recognition of carboxylic acids and phosphonic acid derivatives. The diguanidine 1a forms 1:1 complexes with the dicarboxylic acids and the diphosphonic acid derivatives in a DMSO solution, and the formation of these complexes was confirmed by a DOSY NMR analysis. The binding mode towards the guanidyl group (Type I, Type II, two existing types of binding modes toward three nitrogen atoms) with a diphosphonic acid derivative was successfully demonstrated by the 2D NOESY analysis. The diguanidine 1a does not show any fluorescence in a DMSO solution, but after the addition of carboxylic acids, the formation of a stable complex or the formation of the protonated guanidinium (1a+2H⁺) were distinguishable by the observation of a light-blue fluorescence around 430 nm. These fluorescence observations can be determined the stability of the complexes of the diguanidine 1a with carboxylic acids. On the other hand, the DMSO solution of diguanidine 1a showed a light-blue fluorescence after the addition of phosphonic acids. Interestingly, diguanidine 1a recognized methylphosphonic acid 9a in the solid state by grinding and showed a green fluorescence, while the other phosphonic acids 9 and dicarboxylic acids (4d: pimelic acid, 4f: azelaic acid) showed a light-blue fluorescence in the solid state, and a selectivity was observed. These fluorescence characteristics of the diguanidine 1 are applicable for the detection of carboxylic acids and phosphonic acids, especially for methylphosphonic acid 9a in the solid state.