Metal cluster-based functional porous coordination polymers

• This review focuses on metal cluster-based porous coordination polymers (PCPs).
• Cluster-based PCPs have various important and modifiable functionalities.
• Post-synthetic modification can improve the functionality of cluster-based PCPs.

This review focuses on a particular class of porous coordination polymers (PCPs) called metal cluster-based PCPs, which are constructed by linking versatile polynuclear clusters as secondary building units via organic linkers. These types of PCPs provide a unique platform for systematically studying the correlations among structure–property relationships and for developing new functional PCP materials with improved properties due to their various advantages, such as their diverse components, stable frameworks, highly predictable topologies, controllable structural flexibility, and various modifiable functionalities. In this review, we highlight and discuss selected examples of cluster-based PCPs, the functionalities of which benefit from either the clusters themselves or their cooperation with linkers, such as gas adsorption, heterogeneous catalysis, magnetism, flexibility, and luminescent sensing, as well as modulations of these functionalities via post-synthetic modifications of the cluster building units.

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