Direct Observation of Intermediates in a Thermodynamically Controlled Solid-State Dynamic Covalent Reaction

Belenguer, Ana M. and Lampronti, Giulio I. and Wales, David J. and Sanders, Jeremy K. M. (2014) Direct Observation of Intermediates in a Thermodynamically Controlled Solid-State Dynamic Covalent Reaction. Journal of the American Chemical Society, 136 (46). pp. 16156-16166. ISSN 0002-7863 Web Edition ISSN: 1520-5126 DOI 10.1021/ja500707z

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Official URL: http://pubs.acs.org/doi/abs/10.1021/ja500707z

Abstract

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 homodimers 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.

Item Type: Article
Uncontrolled Keywords: 2014AREP; IA67
Subjects: 03 - Mineral Sciences
Divisions: 03 - Mineral Sciences
Journal or Publication Title: Journal of the American Chemical Society
Volume: 136
Page Range: pp. 16156-16166
Identification Number: 10.1021/ja500707z
Depositing User: Giulio Isacco Lampronti
Date Deposited: 20 Aug 2015 15:04
Last Modified: 20 Aug 2015 15:04
URI: http://eprints.esc.cam.ac.uk/id/eprint/3448

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