Anion binding properties of indolylmethanes

The anion binding properties of the indolylmethanes (1) were investigated by 1H-NMR spectroscopy in CDCl3. Tris(3-methylindol-2-yl)methane (1a) selectively bound a chloride anion the over other tested anions (Br−, I−, HSO4−, and NO3−). In contrast, analogous compounds, phenyl bis(3-methylindol-2-yl)methane (1b), 2-hydroxyphenyl bis(3-methylindol-2-yl)methane (1c), tri(indol-3-yl)methane (1d), and phenyl di(indol-2-yl)methane (1e), showed a low anion binding ability and selectivity. These results indicate that the number and a position of the binding sites (indole NH protons) of the indolylmethanes are important factors for the formation of the complex with an anion. The high binding ability and selectivity of 1a toward a chloride anion is attributed to the proper size of the binding pocket for a chloride anion and the formation of multiple hydrogen bonds between the three indole NH protons and a chloride anion. The anion affinity of 1a was significantly affected by the cation component of quaternary ammonium salts, indicating that it is ion pair binding and not solely anion binding.