Functional crystalline porous framework materials based on supramolecular macrocycles

Crystalline porous framework materials like metal–organic frameworks (MOFs) and covalent–organic frameworks (COFs) possess periodic extended structures, high porosity, tunability and designability, making them good candidates for sensing, catalysis, gas adsorption, separation, etc. Despite their many advantages, there are still problems affecting their applicability. For example, most of them lack specific recognition sites for guest uptake. Supramolecular macrocycles are typical hosts for guest uptake in solution. Macrocycle-based crystalline porous framework materials, in which macrocycles are incorporated into framework materials, are growing into an emerging area as they combine reticular chemistry and supramolecular chemistry. Organic building blocks which incorporate macrocycles endow the framework materials with guest recognition sites in the solid state through supramolecular interactions. Distinct from solution-state molecular recognition, the complexation in the solid state is ordered and structurally achievable. This allows for determination of the mechanism of molecular recognition through noncovalent interactions while that of the traditional recognition in solution is ambiguous. Furthermore, crystalline porous framework materials in the solid state are well-defined and recyclable, and can realize what is impossible in solution. In this review, we summarize the progress of the incorporation of macrocycles into functional crystalline porous frameworks (i.e., MOFs and COFs) for their solid state applications such as molecular recognition, chiral separation and catalysis. We focus on the design and synthesis of organic building blocks with macrocycles, and then illustrate the applications of framework materials with macrocycles. Finally, we propose the future directions of macrocycle-based framework materials as reliable carriers for specific molecular recognition, as well as guiding the crystalline porous frameworks with their chemistry, applications and commercialization.