Consecutive single-crystal-to-single-crystal isomerization of novel octamolybdate anions within a microporous hybrid framework with robust water sorption properties
The 3D hybrid framework [{Cu(cyclam)}3(kMo8O27)]· 14H2O (1) (cyclam=1,4,8,11-tetraazacyclotetradecane) undergoes sequential single-crystal-to-singlecrystal transformations upon heating to afford two different anhydrous phases (2 a and 3a). These transitions modify the framework dimensionality and en...
| Autores: | , , , , , , , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2023 |
| País: | España |
| Institución: | Universidad Pública de Navarra |
| Repositorio: | Academica-e. Repositorio Institucional de la Universidad Pública de Navarra |
| OAI Identifier: | oai:academica-e.unavarra.es:2454/46649 |
| Acceso en línea: | https://hdl.handle.net/2454/46649 |
| Access Level: | acceso abierto |
| Palabra clave: | Microporous Materials Polyoxometalates Single-Crystal-to-Single-Crystal Solid-State Isomerization Water Sorption |
| Sumario: | The 3D hybrid framework [{Cu(cyclam)}3(kMo8O27)]· 14H2O (1) (cyclam=1,4,8,11-tetraazacyclotetradecane) undergoes sequential single-crystal-to-singlecrystal transformations upon heating to afford two different anhydrous phases (2 a and 3a). These transitions modify the framework dimensionality and enable the isomerization of k-octamolybdate (k-Mo8) anions into λ (2 a) and μ (3 a) forms through metal migration. Hydration of 3 a involves condensation of one water molecule to the cluster to afford the γ-Mo8 isomer in 4, which dehydrates back into 3a through the 6a intermediate. In contrast, 2a reversibly hydrates to form 5, exhibiting the same Mo8 cluster as that of 1. It is remarkable that three of the Mo8 clusters (k, λ and μ) are new and that up to three different microporous phases can be isolated from 1 (2 a, 3a, and 6a). Water vapor sorption analyses show high recyclability and the highest uptake values for POM-based systems. The isotherms display an abrupt step at low humidity level desirable for humidity control devices or water harvesting in drylands. |
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