Exploiting 1,4-naphthoquinone and 3-iodo-1,4-naphthoquinone motifs as anion binding sites by hydrogen or halogen-bonding interactions

We describe here the utilization of 1,4-naphthoquinone and 3-iodo-1,4-naphthoquinone motifs as new anion binding sites by hydrogen- or halogen-bonding interactions, respectively. These binding sites have been integrated in bidentate ester based receptors. Emission experiments reveal that both receptors selectively recognize sulfate anions, which induced a remarkable increase of a new emission band attributed to the formation of -stacking interactions between two 1,4-naphthoquinone units. Absorption spectroscopy and mass spectrometry indicate the disruption of the ester group of the 1,4-naphthoquinone based receptor in the presence of HP 2 O 7 3 , H 2 PO 4 , F , AcO and C 6 H 5 CO 2 and in the halogenated receptor with HP 2 O 7 3 , F and AcO anions, while the presence of sulfate anions showed the clasical complexation behaviour. The 1 H-NMR experiment showed a slow exchange process of the receptors with their sulfate complexes. The binding mode of the receptors with sulfate has been studied by DFT calculations along with the Molecular Electrostatic Potential (MEP) surface computational tool that reveals those parts of the receptors which are more suitable for interacting with anions. 1,4-Naphthoquinone and 3-iodo-1,4-naphthoquinone have been explored as hydrogen- or halogen-binding sites for anions integrated in ester based receptors which selectively recognize sulfate anions.