Sequential Linker Installation in Metal-Organic Frameworks

ConspectusMetal-organic frameworks (MOFs) represent a sophisticated blend of inorganic and organic components, promoting the development of coordination chemistry greatly and offering a versatile platform for tailored functionalities. By combining various metal nodes, organic linkers, and functional guests, MOFs provide numerous pathways for their design, synthesis, and customization. Among these, sequential linker installation (SLI) stands out as a novel and crucial strategy, enabling the precise integration of desired properties and functions at the atomic scale. SLI enhances structural diversity and stability while facilitating the meticulous construction of robust frameworks by leveraging open metal sites and functional organic linkers at targeted locations. Compared to the direct synthesis of MOFs, postsynthetic modification methods allow for precise regulation of their structures and corresponding properties. While unlike conventional postsynthetic modification methods, SLI requires the careful selection of linkers and framework design to ensure precise positioning for installation, which gives rise to the well-designed and ordered positions for the installed linkers, confirmed directly by X-ray diffraction technology.Recent advancements in MOF synthesis have led to the creation of increasingly tailored flexible matrix structures, particularly due to the diverse connection modes of multicore metal clusters, especially for the Zr₆ cluster. The spatial hindrance of certain ligands has resulted in the formation of unsaturated metal clusters and various missing linker pockets. Examples of these advanced MOFs include PCN-606, PCN-608, PCN-609, PCN-700, and PCN-808, which feature specific open metal sites and certain framework flexibility conducive to SLI. Strategically positioned open metal sites within these frameworks serve as predetermined anchor points for desired functional molecules, while the frameworks' flexibility can accommodate molecules of varying sizes to a certain extent, enlarging the scopes of application greatly. This precise positioning of functional groups enables the creation of tailored sites for enhanced applications, such as adsorption, catalysis, and recognition.In this Account, we delve into the intricate process of designing and synthesizing MOFs with appropriate missing-linker pockets for the aforementioned applications. We discuss the meticulous selection of functional linkers and the methods used to insert them into the corresponding missing-linker pockets within the MOFs. Additionally, we explore the diverse properties and functionalities of the resulting MOFs, focusing on their adsorptive, catalytic, and recognition performance. Furthermore, we provide insights into the future trajectory of SLI methods, complemented by our recent works. This Account not only reviews the evolution of the SLI method but also underscores its practical applications across various functional domains, paving a rational pathway for the future development of advanced multifunctional MOFs through this method.