Porous Nanosheet Assembly for Macrocyclization and Self-Release.

Macrocyclic structures are challenging synthetic targets owing to various potential applications ranging from drug discovery to nanomaterials. Their use, however, is highly limited due to synthetic difficulties arising from an entropic penalty for folding of linear chains. Here, we report single-layered porous nanosheets with 2D ordered internal cavities that act as a highly efficient macrocycle generator, changing linear substrates to release as macrocycles in aqueous methanol solution. The nanosheets with hydrophobic cavities encapsulate a linear substrate with nearly perfect uptake, perform clean cyclization, and then spontaneously release as a pure macrocycle. The self-separation of the macrocycle that precipitates from the solution leads to repeated cycles of macrocycle generation; thereby, the single-layered porous materials enabling catch and release offer a powerful novel strategy for repeated macrocycle generation.