Journal of the American Chemical Society · 2020 · 51 citations · 61 references
Natural SciencesChemistryMaterials ScienceCrystal StructureNanomaterialsStructural BiologyMacromolecular AssemblySelf-assembled NanostructuresSelf-assemblySelf-assembly Of NanomaterialsSupramolecular MaterialsHierarchical Assembly PathwaysHierarchical Self-assemblyLigand DesignMetal-organic Supramolecular AssembliesMixed Solvent SystemsSelf-assembly In Host-guest SystemsTetrahedral ComplexesTetrahedral Coordination
The artificial synthesis of giant, three-dimensional, and shell-like architectures with growing complexity and novel functionalities is an especially challenging task for chemists. Fullerenes and self-assembled cages are remarkable examples that are proven milestones in the field of functional materials. Herein, we present another unique system: a giant terpyridine-based truncated metallo-tetrahedral architecture that includes densely-packed ionic pairs with a significant internal cavity. This huge metallo-tetrahedron with a molecular weight up to 70 000 Da was self-assembled simultaneously with 64 components: 12 large antler-shaped ligands (5), 4 star-shaped ligands (6), and 48 Cd2+ ions. Surprisingly, the giant tetrahedron shows broad visible emission (400–640 nm) and aggregation induced emission enhancement (AIEE) via a hierarchical assembly into highly-ordered nanoaggregates. A tunable emission color and near white-light emission in mixed solvent systems were also achieved. The present work not only affords an effective approach to the creation of giant shell-like architectures that can be used to mimic biological viruses and chemical frameworks but also provides a new class of functional metallo-architectures.
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