Dynamic Interconversion and Induced-Fit Guest Binding with Two Macrocycle-Based Coordination Cages.

We report the syntheses and host-guest chemistry of two interconvertible coordination cages, Pd 2 L 2 and Pd 1 L 1 , from a dynamic macrocycle ligand (L) and a cis-blocking (tmen)Pd(NO 3 ) 2 (tmen = tetramethylethylenediamine) unit (Pd). The water-soluble macrocyclic L, which can bind various polycyclic aromatic hydrocarbon (PAH) guests in its cis-conformation, was constructed via four pyridinium bonds between two 2,4,6-tri(4-pyridyl)-1,3,5-triazine [TPT] panels and two p -xylene bridges. We selectively formed each cage either by changing the reaction concentration/solvent/temperature or through induced-fit guest encapsulation, while direct assembly of L and Pd resulted in a mixture of Pd 2 L 2 and Pd 1 L 1 in equilibrium. X-ray structures of the free ligand and the host-guest complexes confirmed the induce-fit adaptive changes in the ligand's conformation and the cage's cavity. This work demonstrates a useful strategy for designing multistimuli-responsive supramolecular hosts by coordination self-assembly with macrocyclic ligands featuring rich conformational freedom.