Biphen[n]arenes: Modular Synthesis, Customizable Cavity Sizes, and Diverse Skeletons

Area of Science:

• Supramolecular Chemistry
• Organic Synthesis
• Materials Science

Background:

• Traditional macrocycles like cyclodextrins have limited cavity sizes ( < 10 Å) and rigid structures.
• Existing macrocycles struggle to accommodate large molecules and lack backbone tunability.
• There is a need for novel macrocyclic frameworks with adjustable dimensions and functional diversity.

Purpose of the Study:

• To develop a versatile and modular strategy for synthesizing novel macrocycles, termed biphenarenes.
• To create macrocycles with customizable cavity sizes and diverse, functionalizable backbones.
• To explore the host-guest properties and potential applications of this new macrocycle family.

Main Methods:

• A modular synthesis approach involving Suzuki-Miyaura coupling to create functionalized monomers.
• Friedel-Crafts alkylation to link monomers and form biphenarene macrocycles (n=3-8).
• Utilizing rigid oligo(para-phenylene) units to construct macrocycles with larger cavities.

Main Results:

• Successful synthesis of biphenarenes with tunable cavity sizes and functional backbones.
• Demonstrated recognition properties for both small molecules and large polypeptides.
• Exhibited peculiar self-assembly behaviors and potential in gas chromatography and pollutant capture.

Conclusions:

• Biphenarenes represent a promising new class of macrocycles with significant potential in supramolecular chemistry.
• The modular synthesis allows for broad customization, expanding the supramolecular toolbox.
• Further research into biphenarenes could lead to advancements in biology, pharmaceutical science, and materials science.