A Modular Synthetic Strategy for Functional Macrocycles

TLDR

The authors present a molecule‑Lego one‑pot, high‑yielding condensation strategy for synthesizing macrocycles with functional skeletons from bis(2,4‑dimethoxyphenyl)arene monomers and paraformaldehyde. By varying the monomer blocks, diverse functional units such as naphthalene, pyrene, anthraquinone, and porphyrin can be incorporated into the macrocycle backbone. Macrocyclization is governed by monomer geometry—linear monomers form trimers and pentamers, while V‑shaped monomers yield dimers—and heterogeneous macrocycles can be produced in moderate yield, indicating promising future applications.

Abstract

Abstract 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.