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Post-synthetic modifications of metal–organic cages

Abstract

Metal–organic cages (MOCs) are discrete, supramolecular entities that consist of metal nodes and organic linkers, which can offer solution processability and high porosity. Thereby, their predesigned structures can undergo post-synthetic modifications (PSMs) to introduce new functional groups and properties by modifying the linker, metal node, pore or surface environment. This Review explores current PSM strategies used for MOCs, including covalent, coordination and noncovalent methods. The effects of newly introduced functional groups or generated complexes upon the PSMs of MOCs are also detailed, such as improving structural stability or endowing desired functionalities. The development of the aforementioned design principles has enabled systematic approaches for the development and characterization of families of MOCs and, thereby, provides insight into structure–function relationships that will guide future developments.

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Fig. 1: The chronological development in post-synthetic modifications of metal–organic cages with representative examples.
Fig. 2: Strategies for post-synthetic modifications of metal–organic cages and the targeted properties.
Fig. 3: Post-synthetic modification from 0D cages to 0D cages by covalent strategies.
Fig. 4: Post-synthetic modification from 0D cages to 0D cages by covalent or coordination strategies.
Fig. 5: Coordination and noncovalent post-synthetic modifications from 0D cages to 0D cages, and 0D cages to 1D or 2D structures.
Fig. 6: Covalent crosslinking of 0D cages to form 3D polymeric materials.
Fig. 7: Post-synthetic assembly of 0D cages into 3D networks by coordination modifications.
Fig. 8: Post-assembly of 0D cages into 3D structures by noncovalent post-synthetic modifications.

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Acknowledgements

This work was supported by National Natural Science Foundation of China (21971126) and National Key R&D Program of China (2018YFA0901800).

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J.L. and Z.W. researched the literature for the Review. J.L. wrote the first version of the manuscript. J.L. and Z.W. prepared the figures. All authors contributed to the discussion and editing of the manuscript before submission.

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Liu, J., Wang, Z., Cheng, P. et al. Post-synthetic modifications of metal–organic cages. Nat Rev Chem 6, 339–356 (2022). https://doi.org/10.1038/s41570-022-00380-y

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