Control of the hierarchical self-assembly of polyoxometalate-based metallomacrocycles by redox trigger and solvent composition
| Autor: | Madeleine, Piot, Benjamin, Abécassis, Dalil, Brouri, Claire, Troufflard, Anna, Proust, Guillaume, Izzet |
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| Rok vydání: | 2018 |
| Předmět: | |
| Zdroj: | Proceedings of the National Academy of Sciences of the United States of America |
| ISSN: | 1091-6490 |
| Popis: | Significance Hierarchical self-assembly is a powerful route allowing the elaboration of complex supramolecular architectures with emergent structuration or properties. Starting from well-defined molecular building units, this synthetic strategy relies on the construction of a preassembled structural motif that can further self-assemble through additional noncovalent interactions. In this context, we developed a system based on a covalent organic–inorganic polyoxometalate hybrid building block combining metal-driven self-assembly and electrostatic interactions. We herein show that in this system, the supramolecular organization can be controlled by a redox stimulus and/or the solvent composition giving rise to various types of nanoarchitectures from discrete metallomacrocycles to 1D worm-like nanoobjects. Discrete metallomacrocycles are attractive scaffolds for the formation of complex supramolecular architectures with emergent properties. We herein describe the formation of hierarchical nanostructures using preformed metallomacrocycles by coordination-driven self-assembly of a covalent organic–inorganic polyoxometalate (POM)-based hybrid. In this system, we take advantage of the presence of charged subunits (POM, metal linker, and counterions) within the metallomacrocycles, which drive their aggregation through intermolecular electrostatic interactions. We show that the solvent composition and the charge of the metal linker are key parameters that steer the supramolecular organization. Different types of hierarchical self-assemblies, zero-dimensional (0D) dense nanoparticles, and 1D worm-like nanoobjects, can be selectively formed owing to different aggregation modes of the metallomacrocycles. Finally, we report that the worm-like structures drastically enhance the solubility in water of a pyrene derivative and can act as molecular carriers. |
| Databáze: | OpenAIRE |
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