Abstract
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+.
Selective M+ binding. A new imine-based cage has been synthesized that acts as a tritopic receptor by binding small alkali metal cations (Li+, Na+) on the outside and large alkali metal cations (Rb+, Cs+) on the inside of the cage (see figure). Association constants were determined for various alkali metal salts and a negative heterotopic cooperative effect between two different binding sites was observed.
