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Coarse-grained modelling to predict the packing of porous organic cages

How molecules pack has vital ramifications for their applications as functional molecular materials. Small changes in a molecule's functionality can lead to large, non-intuitive, changes in their global solid-state packing, resulting in difficulty in targeted design. Predicting the crystal stru...

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Autores principales: Wolpert, Emma H., Jelfs, Kim E.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9683088/
https://www.ncbi.nlm.nih.gov/pubmed/36507173
http://dx.doi.org/10.1039/d2sc04511g
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author Wolpert, Emma H.
Jelfs, Kim E.
author_facet Wolpert, Emma H.
Jelfs, Kim E.
author_sort Wolpert, Emma H.
collection PubMed
description How molecules pack has vital ramifications for their applications as functional molecular materials. Small changes in a molecule's functionality can lead to large, non-intuitive, changes in their global solid-state packing, resulting in difficulty in targeted design. Predicting the crystal structure of organic molecules from only their molecular structure is a well-known problem plaguing crystal engineering. Although relevant to the properties of many organic molecules, the packing behaviour of modular porous materials, such as porous organic cages (POCs), greatly impacts the properties of the material. We present a novel way of predicting the solid-state phase behaviour of POCs by using a simplistic model containing the dominant degrees of freedom driving crystalline phase formation. We employ coarse-grained simulations to systematically study how chemical functionality of pseudo-octahedral cages can be used to manipulate the solid-state phase formation of POCs. Our results support those of experimentally reported structures, showing that for cages which pack via their windows forming a porous network, only one phase is formed, whereas when cages pack via their windows and arenes, the phase behaviour is more complex. While presenting a lower computational cost route for predicting molecular crystal packing, coarse-grained models also allow for the development of design rules which we start to formulate through our results.
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spelling pubmed-96830882022-12-08 Coarse-grained modelling to predict the packing of porous organic cages Wolpert, Emma H. Jelfs, Kim E. Chem Sci Chemistry How molecules pack has vital ramifications for their applications as functional molecular materials. Small changes in a molecule's functionality can lead to large, non-intuitive, changes in their global solid-state packing, resulting in difficulty in targeted design. Predicting the crystal structure of organic molecules from only their molecular structure is a well-known problem plaguing crystal engineering. Although relevant to the properties of many organic molecules, the packing behaviour of modular porous materials, such as porous organic cages (POCs), greatly impacts the properties of the material. We present a novel way of predicting the solid-state phase behaviour of POCs by using a simplistic model containing the dominant degrees of freedom driving crystalline phase formation. We employ coarse-grained simulations to systematically study how chemical functionality of pseudo-octahedral cages can be used to manipulate the solid-state phase formation of POCs. Our results support those of experimentally reported structures, showing that for cages which pack via their windows forming a porous network, only one phase is formed, whereas when cages pack via their windows and arenes, the phase behaviour is more complex. While presenting a lower computational cost route for predicting molecular crystal packing, coarse-grained models also allow for the development of design rules which we start to formulate through our results. The Royal Society of Chemistry 2022-10-25 /pmc/articles/PMC9683088/ /pubmed/36507173 http://dx.doi.org/10.1039/d2sc04511g Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/
spellingShingle Chemistry
Wolpert, Emma H.
Jelfs, Kim E.
Coarse-grained modelling to predict the packing of porous organic cages
title Coarse-grained modelling to predict the packing of porous organic cages
title_full Coarse-grained modelling to predict the packing of porous organic cages
title_fullStr Coarse-grained modelling to predict the packing of porous organic cages
title_full_unstemmed Coarse-grained modelling to predict the packing of porous organic cages
title_short Coarse-grained modelling to predict the packing of porous organic cages
title_sort coarse-grained modelling to predict the packing of porous organic cages
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9683088/
https://www.ncbi.nlm.nih.gov/pubmed/36507173
http://dx.doi.org/10.1039/d2sc04511g
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