The construction of solid‐state fluorescent materials with high quantum yield and good processability is of vital importance in the preparation of organic light‐emitting devices. Herein, a series of tetraphenylethylene (TPE)‐based multicomponent emissive metallacages are prepared by the coordination‐driven self‐assembly of tetra‐(4‐pyridylphenyl)ethylene, cis‐Pt(PEt3)2(OTf)2 and tetracarboxylic ligands. These metallacages exhibit good emission both in solution and in the solid state because the coordination bonds and aggregation restrict the molecular motions of TPE synergistically, which suppresses the non‐radiative decay of these metallacages. Impressively, one of the metallacages achieves very high fluorescence quantum yield (ΦF=88.46 %) in the solid state, which is further used as the coatings of a blue LED bulb to achieve white‐light emission. The study not only provides a general method to the preparation of TPE‐based metallacages but also explores their applications as solid‐state fluorescent materials, which will promote the future design and applications of metallacages as useful emissive devices.

We herein report the preparation of a series of hexaphenylbenzene (HPB)-based deep blue-emissive metallacages via multicomponent coordination-driven self-assembly. These metallacages feature prismatic structures with HPB derivatives as the faces and tetracarboxylic ligands as the pillars, as evidenced by NMR, mass spectrometry and X-ray diffraction analysis. Light-harvesting systems were further constructed by employing the metallacages as the donor and a naphthalimide derivative (NAP) as the acceptor, owing to their good spectral overlap. The judiciously chosen metallacage serves as the antenna, providing the suitable energy to excite the non-emissive NAP, and thus resulting in bright emission for NAP in the solid state. This study provides a type of HPB-based multicomponent emissive metallacage and explores their applications as energy donors to light up non-emissive fluorophores in the solid state, which will advance the development of emissive metallacages as useful luminescent materials.

The development of supramolecular hosts with effective host–guest properties is crucial for their applications. Herein, we report the preparation of a porphyrin-based metallacage, which serves as a host for a series of polycyclic aromatic hydrocarbons (PAHs). The association constant between the metallacage and coronene reaches 2.37 × 10 7 M –1 in acetonitrile/chloroform (ν/ν = 9/1), which is among the highest values in metallacage-based host–guest complexes. Moreover, the metallacage exhibits good singlet oxygen generation capacity, which can be further used to oxidize encapsulated anthracene derivatives into anthracene endoperoxides, leading to the release of guests. By employing 10-phenyl-9-(2-phenylethynyl)anthracene whose endoperoxide can be converted back by heating as the guest, a reversible controlled release system is constructed. This study not only gives a type of porphyrin-based metallacage that shows desired host–guest interactions with PAHs but also offers a photooxidation-responsive host–guest recognition motif, which will guide future design and applications of metallacages for stimuli-responsive materials.

The construction of solid‐state fluorescent materials with high quantum yield and good processability is of vital importance in the preparation of organic light‐emitting devices. Herein, a series of tetraphenylethylene (TPE)‐based multicomponent emissive metallacages are prepared by the coordination‐driven self‐assembly of tetra‐(4‐pyridylphenyl)ethylene, cis‐Pt(PEt3)2(OTf)2 and tetracarboxylic ligands. These metallacages exhibit good emission both in solution and in the solid state because the coordination bonds and aggregation restrict the molecular motions of TPE synergistically, which suppresses the non‐radiative decay of these metallacages. Impressively, one of the metallacages achieves very high fluorescence quantum yield (ΦF=88.46 %) in the solid state, which is further used as the coatings of a blue LED bulb to achieve white‐light emission. The study not only provides a general method to the preparation of TPE‐based metallacages but also explores their applications as solid‐state fluorescent materials, which will promote the future design and applications of metallacages as useful emissive devices.

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 selfhealing and shape memory materials, which will promote the study of metallacage-cored supramolecular networks as smart materials.