Shape-Selective Crystallisation of Fluxional Carbon Cages

Bismillah, A.N.; Sturala, J.; Chapin, B.M.; Yufit, D.S.; Hodgkinson, P.; McGonigal, P.R.

doi:10.1039/c8sc04303e

Shape-Selective Crystallisation of Fluxional Carbon Cages

Bismillah, A.N.; Sturala, J.; Chapin, B.M.; Yufit, D.S.; Hodgkinson, P.; McGonigal, P.R.

Authors

A.N. Bismillah

J. Sturala

B.M. Chapin

Dr Dmitry Yufit d.s.yufit@durham.ac.uk
Academic Visitor

Professor Paul Hodgkinson paul.hodgkinson@durham.ac.uk
Professor

Dr Paul Mcgonigal paul.mcgonigal@durham.ac.uk
Academic Visitor

Abstract

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.

Citation

Bismillah, A., Sturala, J., Chapin, B., Yufit, D., Hodgkinson, P., & McGonigal, P. (2018). Shape-Selective Crystallisation of Fluxional Carbon Cages. Chemical Science, 9(46), 8631-8636. https://doi.org/10.1039/c8sc04303e

Journal Article Type	Article
Acceptance Date	Oct 19, 2018
Online Publication Date	Oct 22, 2018
Publication Date	Dec 14, 2018
Deposit Date	Jul 30, 2018
Publicly Available Date	Nov 29, 2018
Journal	Chemical Science
Print ISSN	2041-6520
Electronic ISSN	2041-6539
Publisher	Royal Society of Chemistry
Peer Reviewed	Peer Reviewed
Volume	9
Issue	46
Pages	8631-8636
DOI	https://doi.org/10.1039/c8sc04303e