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On/off porosity switching and post-assembly modifications of Cu(4)L(4) metal–organic polyhedra
Synthetic porous materials composed of metal–organic polyhedra (MOPs) have found application in topical areas such as gas storage, separation and catalysis. Control over their physical properties (e.g. porosity) has typically been achieved through ligand design or judicious choice of metal ions. Her...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8152621/ https://www.ncbi.nlm.nih.gov/pubmed/34094054 http://dx.doi.org/10.1039/d0sc00070a |
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author | Bloch, Witold M. Babarao, Ravichandar Schneider, Matthew L. |
author_facet | Bloch, Witold M. Babarao, Ravichandar Schneider, Matthew L. |
author_sort | Bloch, Witold M. |
collection | PubMed |
description | Synthetic porous materials composed of metal–organic polyhedra (MOPs) have found application in topical areas such as gas storage, separation and catalysis. Control over their physical properties (e.g. porosity) has typically been achieved through ligand design or judicious choice of metal ions. Here, we demonstrate pore-size control and on/off porosity in Cu(4)L(4) MOPs by exploiting their structural non-rigidity. We report an aldehyde-functionalised MOP (1) that can be isolated in five distinct solvatomorphs, each exhibiting different structural flexibility. When soaked in MeOH, two of these solvatomorphs undergo a rapid transformation to a thermodynamically favoured phase, whilst in acetone they template the crystallisation of an entirely new crystal packing. We support these findings by single and powder X-ray diffraction and rationalise the observed phase transformations by lattice energy calculations. Of the five solvatomorphs, three can be obtained as solvent-exchanged pseudo-polymorphs with distinct porosities in their activated form (SA(BET) = 35–455 m(2) g(−1)). Further control over the crystal packing of MOPs is achieved through covalent post-assembly modifications, which promote the crystallisation of isoreticular 2-D sheet-like structures. |
format | Online Article Text |
id | pubmed-8152621 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-81526212021-06-03 On/off porosity switching and post-assembly modifications of Cu(4)L(4) metal–organic polyhedra Bloch, Witold M. Babarao, Ravichandar Schneider, Matthew L. Chem Sci Chemistry Synthetic porous materials composed of metal–organic polyhedra (MOPs) have found application in topical areas such as gas storage, separation and catalysis. Control over their physical properties (e.g. porosity) has typically been achieved through ligand design or judicious choice of metal ions. Here, we demonstrate pore-size control and on/off porosity in Cu(4)L(4) MOPs by exploiting their structural non-rigidity. We report an aldehyde-functionalised MOP (1) that can be isolated in five distinct solvatomorphs, each exhibiting different structural flexibility. When soaked in MeOH, two of these solvatomorphs undergo a rapid transformation to a thermodynamically favoured phase, whilst in acetone they template the crystallisation of an entirely new crystal packing. We support these findings by single and powder X-ray diffraction and rationalise the observed phase transformations by lattice energy calculations. Of the five solvatomorphs, three can be obtained as solvent-exchanged pseudo-polymorphs with distinct porosities in their activated form (SA(BET) = 35–455 m(2) g(−1)). Further control over the crystal packing of MOPs is achieved through covalent post-assembly modifications, which promote the crystallisation of isoreticular 2-D sheet-like structures. The Royal Society of Chemistry 2020-03-05 /pmc/articles/PMC8152621/ /pubmed/34094054 http://dx.doi.org/10.1039/d0sc00070a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Bloch, Witold M. Babarao, Ravichandar Schneider, Matthew L. On/off porosity switching and post-assembly modifications of Cu(4)L(4) metal–organic polyhedra |
title | On/off porosity switching and post-assembly modifications of Cu(4)L(4) metal–organic polyhedra |
title_full | On/off porosity switching and post-assembly modifications of Cu(4)L(4) metal–organic polyhedra |
title_fullStr | On/off porosity switching and post-assembly modifications of Cu(4)L(4) metal–organic polyhedra |
title_full_unstemmed | On/off porosity switching and post-assembly modifications of Cu(4)L(4) metal–organic polyhedra |
title_short | On/off porosity switching and post-assembly modifications of Cu(4)L(4) metal–organic polyhedra |
title_sort | on/off porosity switching and post-assembly modifications of cu(4)l(4) metal–organic polyhedra |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8152621/ https://www.ncbi.nlm.nih.gov/pubmed/34094054 http://dx.doi.org/10.1039/d0sc00070a |
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