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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...

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Autores principales: Bismillah, Aisha N., Sturala, Jiri, Chapin, Brette M., Yufit, Dmitry S., Hodgkinson, Paul, McGonigal, Paul R.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2018
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.
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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
title_full Shape-selective crystallisation of fluxional carbon cages
title_fullStr Shape-selective crystallisation of fluxional carbon cages
title_full_unstemmed Shape-selective crystallisation of fluxional carbon cages
title_short Shape-selective crystallisation of fluxional carbon cages
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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