Issue 46, 2018

Shape-selective crystallisation of fluxional carbon cages

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.

Graphical abstract: Shape-selective crystallisation of fluxional carbon cages

Supplementary files

Article information

Article type
Edge Article
Submitted
27 Sept. 2018
Accepted
19 Okt. 2018
First published
22 Okt. 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2018,9, 8631-8636

Shape-selective crystallisation of fluxional carbon cages

A. N. Bismillah, J. Sturala, B. M. Chapin, D. S. Yufit, P. Hodgkinson and P. R. McGonigal, Chem. Sci., 2018, 9, 8631 DOI: 10.1039/C8SC04303E

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