An imine-based molecular cage with distinct binding sites for small and large alkali metal cations

The synthesis of a cylindrical, imine-based cage composed of two trimeric metallamacrocycles is described. The cage acts as a heterotopic receptor for alkali metal cations. The small cations Li(+), Na(+), and K(+) bind to the outside of the cage with good selectivity for Li(+), whereas the larger cations Rb(+) and Cs(+) are bound inside the cage to form unusual π complexes with a good selectivity for Cs(+). Negative heterotopic cooperativity between the two binding sites is observed. The complexation of Cs(+) is associated with a color change, which enables the cage to be used as a specific sensor for Cs(+).