Modular Strategy for Constructing para -Cage[ n ]arenes, meta -Cage[ n ]arenes, and meta -Bimacrocyclic-Arenes.

Here, we present a versatile modular strategy for crafting novel covalent organic cages ( para -cage[ n ]arenes and meta -cage[ n ]arenes, n = 3,4) and bimacrocycles ( meta -bimacrocyclic-arenes) with stable backbones and modifiable rims. These structures can be synthesized from commercially available aromatic multialdehydes in a three-step process: quantitative bromination, Suzuki-Miyaura reaction (yielding over 60%), and a rapid one-pot Friedel-Crafts reaction with paraformaldehyde. Notably, the cage[ n ]arenes exhibit a well-defined prismatic shape, and the bimacrocyclic-arenes display both dimeric and monomeric configurations.