Steric hindrance in metal coordination drives the separation of pyridine regioisomers using rhodium(II)-based metal-organic polyhedra
Hernández López, Laura (Institut Català de Nanociència i Nanotecnologia)
Martínez-Esaín, Jordi (Institut Català de Nanociència i Nanotecnologia)
Carné-Sánchez, Arnau (Institut Català de Nanociència i Nanotecnologia)
Grancha, Thais (Institut Català de Nanociència i Nanotecnologia)
Faraudo, Jordi (Institut de Ciència de Materials de Barcelona)
Maspoch Comamala, Daniel (Institut Català de Nanociència i Nanotecnologia)

Date:	2021
Abstract:	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.
Grants:	Ministerio de Ciencia e Innovación PRE2019-088056 Ministerio de Economía y Competitividad RTI2018-095622-B-I00 Ministerio de Economía y Competitividad SEV-2017-0706 Ministerio de Economía y Competitividad FJCI-2017-31598 Ministerio de Economía y Competitividad IJCI-2016-29802 Agència de Gestió d'Ajuts Universitaris i de Recerca 2017/SGR-238 Agencia Estatal de Investigación CTQ2017-87262-R Agencia Estatal de Investigación EUR2019-103824
Note:	Altres ajuts: it was also funded by the CERCA Programme/Generalitat de Catalunya.
Rights:	Tots els drets reservats.
Language:	Anglès
Document:	Article ; recerca ; Versió acceptada per publicar
Subject:	Liquid liquid-extraction ; Metal-organic polyhedra ; Regioisomers ; Separations ; Steric hindrance
Published in:	Angewandte Chemie (International ed. Internet), Vol. 60, issue 20 (May 2021) , p. 11406-11413, ISSN 1521-3773

DOI: 10.1002/anie.202100091

Postprint 17 p, 1.1 MB

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Research literature > UAB research groups literature > Research Centres and Groups (research output) > Experimental sciences > Catalan Institute of Nanoscience and Nanotechnology (ICN2)
Articles > Research articles
Articles > Published articles