Organo-macrocycle-containing hierarchical metal-organic frameworks and cages: design, structures, and applications

Developing hierarchical ordered systems is challenging. Using organo-macrocycles to construct metal-organic frameworks (MOFs) and porous coordination cages (PCCs) provides an efficient way to obtain hierarchical assemblies. Macrocycles, such as crown ethers, cyclodextrins, calixarenes, cucurbiturils, and pillararenes, can be incorporated within MOFs/PCCs and they also endow the resultant composites with enhanced properties and functionalities. This review summarizes recent developments of organo-macrocycle-containing hierarchical MOFs/PCCs, emphasizing applications and structure-property relationships of these hierarchically porous materials. This review provides insights for future research on hierarchical self-assembly using macrocycles as building blocks and functional ligands to extend the applications of the composites. Organo-macrocycles can directly build metal-organic frameworks (MOFs) and porous coordination cages (PCCs), or be functionalized on them. These hierarchical assemblies extend the properties and functionalities for recognition, adsorption, catalysis, energy storage and so on.