A Modular Synthetic Strategy for Functional Macrocycles.

Area of Science:

• Organic Chemistry
• Supramolecular Chemistry
• Materials Science

Background:

• Macrocycles are important cyclic molecules with diverse applications.
• Developing efficient and versatile synthetic routes for functional macrocycles remains a key challenge in chemistry.

Purpose of the Study:

• To develop a novel "molecule-Lego" synthetic strategy for constructing macrocycles with tunable and functional skeletons.
• To explore the influence of monomer geometry and co-oligomerization on macrocycle formation.

Main Methods:

• One-pot condensation reaction between bis(2,4-dimethoxyphenyl)arene monomers and paraformaldehyde.
• Systematic variation of monomeric blocks to introduce different functional units (e.g., naphthalene, pyrene, anthraquinone, porphyrin).
• Investigation of different geometrical configurations of monomers (linear vs. V-shaped) to control macrocyclization.

Main Results:

• Achieved high-yielding synthesis of macrocycles with diverse functional skeletons.
• Demonstrated that linear monomers yield cyclic trimers and pentamers, while V-shaped monomers favor dimers.
• Successfully synthesized heterogeneous macrocycles through co-oligomerization of different monomers.

Conclusions:

• The molecule-Lego strategy offers a versatile and efficient approach to macrocycle synthesis.
• Monomer geometry is a critical factor in controlling macrocycle size and structure.
• The ability to create heterogeneous macrocycles opens new avenues for designing complex molecular architectures.