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Coordinative supramolecular cages with adjustable cavities have found extensive applications in various fields, but the cavity modification strategies for multi‐functional structures are still challenging. Here, we present a tension‐driven self‐expansion strategy for construction of multi‐cavity cages with high structural complexity. Under the regulation of strain‐induced capping ligands, unprecedented heteromorphosis triple‐cavity cages S2/S4 were obtained based on a metallo‐organic ligand (MOL) scaffold. The heteromorphosis cages exhibited significant higher cavity diversity than the homomorphous double‐cavity cages S1/S3; all of the cages were thoroughly characterized through various analytical techniques including (1D and 2D) NMR, ESI‐MS, TWIM‐MS, AFM, and SAXS analyses. Furthermore, the encapsulation of porphyrin in the cavities of these multi‐cavity cages were investigated. This research opens up new possibilities for the architecture of heteromorphosis supramolecular cages via precisely controlled "scaffold‐capping" assembly with preorganized ligands, which could have potential applications in the development of multifunctional structures with higher complexity. [ABSTRACT FROM AUTHOR]

Fractal structures with self‐similarity are of fundamental importance in the fields of aesthetic, chemistry and mathematics. Here, by taking advantage of constructs the rational geometry‐directed precursor design, we report the construction of two fascinating Platonic solids, the Sierpiński tetrahedron ST‐T and the Sierpiński octahedron ST‐O, in which each possesses a fractal Sierpiński triangle on their independent faces. These two discrete complexes are formed in near‐quantitative yield from the multi‐component self‐assembly of truncated Sierpiński triangular kernel L1 with tribenzotriquinacene‐based hexatopic and anthracene‐based tetratopic terpyridine ligands (L3 and L4) in the presence of metal ions, respectively. The enhanced stabilities of the 3D discrete structures were investigated by gradient tandem mass spectrometry (gMS2). This work provides new constructs for the imitation of complex virus assemblies and for the molecular encapsulation of giant guest molecules. [ABSTRACT FROM AUTHOR]

Coordination‐driven self‐assembly has led to the formation of various aesthetical polyhedrons and compounds with advanced functions. Whereas two‐dimensional supramolecules with complex and giant skeletons are plentiful, the constructions of polyhedrons are limited by using basic polygons as the panels. Herein, we report the modular synthesis of a tessellated triangle and tessellated octahedron with metal‐organic modules as the panels and formed via template‐driven self‐assembly. These architectures have diameters on the order of 10.9 nm and molecular weights greater than 84 kDa. Interestingly, fiber and spherical‐like nanostructures could be formed from the tessellated triangles and octahedrons, respectively, through hierarchical self‐assembly. In addition, after hybridization with carbon nanotubes, the supramolecules exhibit electrochemical reduction activity for CO2 to CO. [ABSTRACT FROM AUTHOR]