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Direct observation of intermediates in a thermodynamically controlled solid-state dynamic covalent reaction.


Type

Article

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Authors

Belenguer, Ana M 
Lampronti, Giulio I 
Wales, David J 
Sanders, Jeremy KM 

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.

Description

Keywords

0306 Physical Chemistry (incl. Structural)

Journal Title

J Am Chem Soc

Conference Name

Journal ISSN

0002-7863
1520-5126

Volume Title

136

Publisher

American Chemical Society (ACS)
Sponsorship
Engineering and Physical Sciences Research Council (EP/J01110X/1)
We are grateful to the EPSRC (AMB, JKMS and DJW) and ERC(DJW) for financial support.