Pillar[6]pyridinium: a hexagonally shaped molecular box that selectively recognizes multicharged anionic species.

A sextuply charged cyclic cationic receptor with an extraordinary structure and unprecedented binding properties is presented. The macrocycle consists of six pyridinium ions connected by methylene linkers with an electron-deficient cavity inside. In the solid state, the cavity is padded with an organized water network that gives the macrocycle a hexagonal shape. In water, the cavity is more flexible and selectively accommodates anionic species. Of the ions of similar size the macrocycle binds most strongly those with the largest negative charge. When the net charge is the same, the most preferred are anions with delocalized charge rather that those with localized charge; remarkably, the former form inclusion complexes, while the latter are complexed externally.