Steric hindrance in metal coordination drives the separation of pyridine regioisomers using rhodium(II)-based metal-organic polyhedra
The physicochemical similarity of isomers makes their chemical separation through conventional techniques energy intensive. Herein, we report that, instead of using traditional encapsulation-driven processes, steric hindrance in metal coordination on the outer surface of Rh-based metal-organic polyh...
| Autores: | , , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2021 |
| País: | España |
| Institución: | Universitat Autònoma de Barcelona |
| Repositorio: | Dipòsit Digital de Documents de la UAB |
| Idioma: | inglés |
| OAI Identifier: | oai:ddd.uab.cat:248679 |
| Acceso en línea: | https://ddd.uab.cat/record/248679 https://dx.doi.org/urn:doi:10.1002/anie.202100091 |
| Access Level: | acceso abierto |
| Palabra clave: | Liquid liquid-extraction Metal-organic polyhedra Regioisomers Separations Steric hindrance |
| Sumario: | The physicochemical similarity of isomers makes their chemical separation through conventional techniques energy intensive. Herein, we report that, instead of using traditional encapsulation-driven processes, steric hindrance in metal coordination on the outer surface of Rh-based metal-organic polyhedra (Rh-MOPs) can be used to separate pyridine-based regioisomers via liquid-liquid extraction. Through molecular dynamics simulations and wet experiments, we discovered that the capacity of pyridines to coordinatively bind to Rh-MOPs is determined by the positions of the pyridine substituents relative to the pyridine nitrogen and is influenced by steric hindrance. Thus, we exploited the differential solubility of bound and non-bound pyridine regioisomers to engineer liquid-liquid self-sorting systems. As a proof of concept, we separated four different equimolecular mixtures of regioisomers, including a mixture of the industrially relevant compounds 2-chloropyridine and 3-chloropyridine, isolating highly pure compounds in all cases. |
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