Reported here is a molecule‐Lego synthetic strategy for macrocycles with functional skeletons, involving one‐pot and high‐yielding condensation between bis(2,4‐dimethoxyphenyl)arene monomers and paraformaldehyde. By changing the blocks, variously functional units (naphthalene, pyrene, anthraquinone, porphyrin, etc.) can be conveniently introduced into the backbone of macrocycles. Interestingly, the macrocyclization can be tuned by the geometrical configuration of monomeric blocks. Linear (180°) monomer yield cyclic trimers and pentamers, while V‐shaped (120°, 90° and 60°) monomers tend to form dimers. More significantly, even heterogeneous macrocycles are obtained in moderate yield by co‐oligomerization of different monomers. This series of macrocycles have the potential to be prosperous in the near future.

Organic crystal engineering is a promising strategy to construct functional materials. Herein, we demonstrate that the marriage of organic crystal engineering and macrocyclic chemistry yields a supramolecular jalousie that can be reversibly opened and closed in crystals. The synchronous rotation of fluorenone units in macrocycles triggered by toluene/phenylmethanol vapor contributes to such motions. This supramolecular jalousie is assembled from a trimeric fluorenone macrocycle, which is synthesized in 46% yield by the condensation of a 2,7-bis­(2,4-dimethoxyphenyl)­fluorenone monomer with paraformaldehyde. Mechanistic studies indicate that the large size (∼1.6 nm) and the rigid skeleton of the trimeric fluorenone macrocycle provide enough space for the rotation of fluorenone units as well as the encapsulation of guests in the solid state. Moreover, the bistable conformations and induced-fit structural adjustment guarantee such switchable single-crystal-to-single-crystal transformations.

A large-cavity carbazole macrocycle (1) is reported through condensation of a long and rigid monomer and paraformaldehyde. 1 exhibits highly selective binding of large-sized tetra(n-propyl) ammonium cation 3+. The complexation...