Interconversion between discrete and a chain of nanocages: self-assembly via a solvent-driven, dimension-augmentation strategy.

Using a ligand bearing a bulky hydrophobic group, a "shish kabob" of nanocages, has been assembled through either a one-fell-swoop or a step-by-step procedure by varying the dielectric constant of the assembly mixture. A hydrophobic solvent breaks down the chain to discrete nanocages, while a hydrophilic solvent reverses the procedure. Although the shish kabob of nanocages has exactly the same chemical composition and even the same Archimedean-solid structure as those of its discrete analogue, its gas-adsorption capacity is remarkably improved because assembly of a chain exposes the internal surface of an individual cage. This dimension-augmentation strategy may have general implications in the preparation of porous materials.