Shape-Selective Crystallisation of Fluxional Carbon Cages

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

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
• Public URL: https://durham-repository.worktribe.com/output/1353474