Inducing Reactivity by Cluster Strain in Titanium Frameworks
[EN] Despite their potential to control charge separation and redox activity, deliberate strategies to distort metal-oxo clusters in molecular frameworks remain limited. Here we present a proof-of-concept for cluster strain engineering using the titanium-organic framework MUV-10 as a model. Replacin...
| Autores: | , , , , , , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2026 |
| País: | España |
| Institución: | Universitat Politècnica de València (UPV) |
| Repositorio: | RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia |
| Idioma: | inglés |
| OAI Identifier: | oai:dnet:riunet______::737d93ec36032cd5d13a068809b44d1e |
| Acceso en línea: | https://riunet.upv.es/handle/10251/233404 |
| Access Level: | acceso abierto |
| Palabra clave: | Metal-organic frameworks Cluster strain engineering Titanium-oxo clusters Goldschmidt tolerance factor Photocatalytic CO2 methanation Redox activity |
| Sumario: | [EN] Despite their potential to control charge separation and redox activity, deliberate strategies to distort metal-oxo clusters in molecular frameworks remain limited. Here we present a proof-of-concept for cluster strain engineering using the titanium-organic framework MUV-10 as a model. Replacing Ca2+ with larger alkaline-earth cations (Sr2+, Ba2+) induces predictable distortions of Ti2M2 clusters and a cubic-to-tetragonal cell transformation while preserving the overall connectivity. This local strain alters Ti-O coordination geometry, enhances ligand-to-metal charge transfer, and promotes the photogeneration of Ti3+ sites, as validated by photocatalytic CO2 methanation under standardized conditions. Importantly, the extent of distortion follows the trend anticipated from the Goldschmidt tolerance factor, a classical descriptor from perovskite chemistry, that we repurpose here to rationalize strain in reticular frameworks. Taken together, these findings establish a conceptual link between oxide catalysis and reticular chemistry, highlighting cluster strain as a potential structural switch to modulate redox reactivity in molecular solids. |
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