Host molecules inside metal–organic frameworks: host@MOF and guest@host@MOF (Matrjoschka) materials

The controllable encapsulation of host molecules (such as porphyrin, phthalocyanine, crown ether, calixarene or cucurbituril organic macrocycles, cages, metal-organic polyhedrons and enzymes) into the pores of metal-organic frameworks (MOFs) to form host-in-host (host@MOF) materials has attracted increasing research interest in various fields. These host@MOF materials combine the merits of MOFs as a host matrix and functional host molecules to exhibit synergistic functionalities for the formation of guest@host@MOF materials in sorption and separation, ion capture, catalysis, proton/ion conduction and biosensors. (This guest@host@MOF construction is reminiscent of Russian (Matrjoschka) dolls which are nested dolls of decreasing size placed one inside another.) In this tutorial review, the advantages of MOFs as a host matrix are presented; the encapsulation approaches and general important considerations for the preparation of host@MOF materials are introduced. The state-of-the-art examples of these materials based on different host molecules are shown, and representative applications and general characterization of these materials are discussed. This review will guide researchers attempting to design functional host@MOF and guest@host@MOF materials for various applications.