Direct observation of intermediates in a thermodynamically controlled solid state dynamic covalent reaction
Journal of the American Chemical Society
American Chemical Society
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Belenguer, A., Lampronti, G. I., Wales, D., & Sanders, J. (2014). Direct observation of intermediates in a thermodynamically controlled solid state dynamic covalent reaction. Journal of the American Chemical Society, 136 16156-16166. https://doi.org/10.1021/ja500707z
We present the first polymorph interconversion study that uses solid state dynamic covalent chemistry (DCC). This system exhibits unexpected and rich behavior, including the observation that under appropriate conditions the polymorph interconversion of a heterodimer proceeds through reversible covalent chemistry intermediates, and this route is facilitated by one of the two disulfide homodimer involved in the reaction. Furthermore, we demonstrate experimentally that in all cases a dynamic equilibrium is reached, meaning that changing the milling conditions affects the free energy difference between the two polymorphs and thus their relative stability. We suggest that this effect is due to the surface solvation energy combined with the high surface to volume ratio of the nanocrystalline powder.
We are grateful to the EPSRC (AMB, JKMS and DJW) and ERC(DJW) for financial support.
External DOI: https://doi.org/10.1021/ja500707z
This record's URL: https://www.repository.cam.ac.uk/handle/1810/246173