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.