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Shape-selective crystallisation of fluxional carbon cages
Dynamic covalent rearrangements of fluxional carbon cages, such as bullvalenes and barbaralanes, impart ‘shapeshifting’ molecular properties. Here, a series of five barbaralanes each interconvert dynamically between two constitutional isomers in solution, but resolve to single isomers upon crystalli...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Royal Society of Chemistry
2018
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6301275/ https://www.ncbi.nlm.nih.gov/pubmed/30647882 http://dx.doi.org/10.1039/c8sc04303e |
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author | Bismillah, Aisha N. Sturala, Jiri Chapin, Brette M. Yufit, Dmitry S. Hodgkinson, Paul McGonigal, Paul R. |
author_facet | Bismillah, Aisha N. Sturala, Jiri Chapin, Brette M. Yufit, Dmitry S. Hodgkinson, Paul McGonigal, Paul R. |
author_sort | Bismillah, Aisha N. |
collection | PubMed |
description | Dynamic covalent rearrangements of fluxional carbon cages, such as bullvalenes and barbaralanes, impart ‘shapeshifting’ molecular properties. Here, a series of five barbaralanes each interconvert dynamically between two constitutional isomers in solution, but resolve to single isomers upon crystallisation. Unexpectedly, the minor solution-phase isomers are resolved in two instances. Through dynamic NMR, crystallographic and DFT analyses, we show that the isomer observed in the solid state is not a direct consequence of the equilibrium distribution in solution or any specific noncovalent interactions. Rather, the dynamic preferential crystallisation is dictated by differences in molecular size and shape. |
format | Online Article Text |
id | pubmed-6301275 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2018 |
publisher | Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-63012752019-01-15 Shape-selective crystallisation of fluxional carbon cages Bismillah, Aisha N. Sturala, Jiri Chapin, Brette M. Yufit, Dmitry S. Hodgkinson, Paul McGonigal, Paul R. Chem Sci Chemistry Dynamic covalent rearrangements of fluxional carbon cages, such as bullvalenes and barbaralanes, impart ‘shapeshifting’ molecular properties. Here, a series of five barbaralanes each interconvert dynamically between two constitutional isomers in solution, but resolve to single isomers upon crystallisation. Unexpectedly, the minor solution-phase isomers are resolved in two instances. Through dynamic NMR, crystallographic and DFT analyses, we show that the isomer observed in the solid state is not a direct consequence of the equilibrium distribution in solution or any specific noncovalent interactions. Rather, the dynamic preferential crystallisation is dictated by differences in molecular size and shape. Royal Society of Chemistry 2018-10-22 /pmc/articles/PMC6301275/ /pubmed/30647882 http://dx.doi.org/10.1039/c8sc04303e Text en This journal is © The Royal Society of Chemistry 2018 http://creativecommons.org/licenses/by-nc/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0) |
spellingShingle | Chemistry Bismillah, Aisha N. Sturala, Jiri Chapin, Brette M. Yufit, Dmitry S. Hodgkinson, Paul McGonigal, Paul R. Shape-selective crystallisation of fluxional carbon cages |
title | Shape-selective crystallisation of fluxional carbon cages
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title_full | Shape-selective crystallisation of fluxional carbon cages
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title_fullStr | Shape-selective crystallisation of fluxional carbon cages
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title_full_unstemmed | Shape-selective crystallisation of fluxional carbon cages
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title_short | Shape-selective crystallisation of fluxional carbon cages
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title_sort | shape-selective crystallisation of fluxional carbon cages |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6301275/ https://www.ncbi.nlm.nih.gov/pubmed/30647882 http://dx.doi.org/10.1039/c8sc04303e |
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