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Multicomponent metallacages can integrate the functions of their different building blocks to achieve synergetic effects for advanced applications. Herein, based on metal‐coordination‐driven self‐assembly, we report the preparation of a series of isoreticular tetraphenylethylene‐based metallacages, which are well characterized by multinuclear NMR, ESI‐TOF‐MS and single‐crystal X‐ray diffraction techniques. The suitable integration of photosensitizing tetraphenylethylene units as faces and Re catalytic complexes as the pillars into a single metallacage offers a high photocatalytic hydrogen production rate of 1707 μmol g−1 h−1, which is one of the highest values among reported metallacages. Femtosecond transient absorption and DFT calculations reveal that the metallacage can serve as a platform for the precise and organized arrangement of the two building blocks, enabling efficient and directional electron transfer for highly efficient photocatalytic performance. This study provides a general strategy to integrate multifunctional ligands into a certain metallacage to improve the efficiency of photocatalytic hydrogen production, which will guide the future design of metallacages towards photocatalysis. [ABSTRACT FROM AUTHOR]

The structures of the crosslinks in supramolecular polymer networks play an important role on their properties and functions. Herein, emissive metallacages are used as crosslinks to prepare metallacage‐cored polyurethanes. The mechanical properties including storage modulus, toughness, Young's modulus and breaking strength of polymers are greatly enhanced with the increase of crosslinking densities. Moreover, such polymers not only exhibit good fluorescence in the solid state, but also show self‐healing and shape memory properties owing to the dynamic reversible non‐covalent bonds in their structures. This study not only offers a convenient strategy to prepare metallacage‐crosslinked networks, but also explores their applications as self‐healing and shape memory materials, which will promote the study of metallacage‐cored supramolecular networks as smart materials. [ABSTRACT FROM AUTHOR]

Supramolecular networks often possess good dynamic features but suffer from low mechanical properties. Supramolecular coordination complexes including metallacycles and metallacages have rigid chemical structures and tunable cavities but often lack processability. Therefore, the reasonable integration of these two types of supramolecular structures into metallacycle/metallacage-cored supramolecular networks will reduce the shortcomings of both structures and offer intriguing properties for diverse applications. This review summarizes the progress of metallacycle/metallacage-cored networks according to the covalent or non-covalent interactions used to connect these metallacycles and metallacages. In each part, the structures, properties, functions and applications of such supramolecular networks are described in detail, in order to demonstrate the most exciting achievements in this emerging area. The remaining challenges and perspectives are also given at the end of this review. We hope this review can give our readers a snapshot on metallacycle/metallacage-cored supramolecular networks and attract more scientists to devote into this promising field. [Display omitted] [ABSTRACT FROM AUTHOR]