Biphen[n]arene-Based Supramolecular Materials

Abstract

Macrocycles play pivotal roles in supramolecular chemistry and materials science because of their distinctive molecular recognition capabilities and versatile applications in self-assembly. However, traditional macrocycles, such as cyclodextrins, calixarenes, cucurbiturils, and pillararenes, have inherent limitations in terms of cavity size and structural variety, which restrict their ability to encapsulate guest molecules of varying sizes and their potential in constructing multifunctional materials. To address these challenges, our group has developed a simple, universal, and modular strategy for constructing functional macrocycles, termed biphen[n]arenes. This approach leverages structure- or function-oriented modular replacement of reactive, functional, and linking modules. Therefore, biphen[n]arenes with customized cavity size and molecule depth can effectively encapsulate guests from small molecules to biomacromolecules. On the other hand, different from modification of side chains, incorporation of functional primitives into the biphen[n]arene scaffold can leave active sites on both edges to induce additional moieties to improve recognition potency or integrate extra application functionality. These characteristics provide significant advantages in the construction of diverse supramolecular materials.