Abstract
We report the syntheses and host-guest chemistry of two interconvertible coordination cages, Pd2L2 and Pd1L1, from a dynamic macrocycle ligand (L) and a cis-blocking (tmen)Pd(NO3)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 Pd2L2 and Pd1L1 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.
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