Nanoconfinement of polyoxometalates in cyclodextrin: computational inspections of the binding affinity and experimental demonstrations of reactivity modulation
Chaotropic polyoxometalates (POMs) form robust host–guest complexes with γ-cyclodextrin (γ-CD), offering promising applications in catalysis, electrochemical energy storage, and nanotechnology. In this article, we provide the first computational insights on the supramolecular binding mechanisms usin...
| Autores: | , , , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2024 |
| País: | España |
| Institución: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositorio: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:2072/537848 |
| Acceso en línea: | http://hdl.handle.net/2072/537848 https://doi.org/10.1039/D4SC01949K |
| Access Level: | acceso abierto |
| Palabra clave: | Química 54 - Química |
| Sumario: | Chaotropic polyoxometalates (POMs) form robust host–guest complexes with γ-cyclodextrin (γ-CD), offering promising applications in catalysis, electrochemical energy storage, and nanotechnology. In this article, we provide the first computational insights on the supramolecular binding mechanisms using density-functional theory and classical molecular dynamics simulations. Focusing on the encapsulation of archetypal Keggin-type POMs (PW12O403−, SiW12O404− and BW12O405−), our findings reveal that the lowest-charged POM, namely PW12O403− spontaneously confines within the wider rim of γ-CD, but BW12O405− does not exhibit this behaviour. This striking affinity for the hydrophobic pocket of γ-CD originates from the structural characteristics of water molecules surrounding PW12O403−. Moreover, through validation using 31P NMR spectroscopy, we demonstrate that this nanoconfinement regulates drastically the POM reactivity, including its capability to undergo electron transfer and intermolecular metalate Mo/W exchanges. Finally, we exploit this nanoconfinement strategy to isolate the elusive mixed addenda POM PW11MoO403−. |
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