Living in the salt-cocrystal continuum: indecisive organic complexes with thermochromic behaviour

Paul Raithby, Charlotte Jones, Jonathan Skelton, Stephen Parker, Aron Walsh, Charles Wilson, Lynne Thomas

Research output: Contribution to journalArticle

3 Citations (Scopus)
26 Downloads (Pure)

Abstract

A family of multicomponent haloaniline/3,5-dinitrobenzoic acid molecular crystals with striking red-to-colourless temperature-induced thermochromism is identified and characterised. Four thermochromic pairs of 1 : 1 neutral cocrystals and ionic salts are identified which, unusually, grow concomitantly under the same conditions. The coloured cocrystals are found to be metastable, kinetically trapped during crystallisation, and convert via proton transfer to the more stable salt forms on heating. The colour of the neutral form and the temperature of the transition can be tuned through the halogen and by chemical substitution on the aniline component. From structural characterisation and first-principles modelling, we elucidate the origin of the metastability of the cocrystals and link structural changes through the phase transition to the striking visible colour change. By deliberately exploiting the uncertainty of the salt-cocrystal continuum, where the small pK a difference between components enables significant solid-state structural rearrangements induced by proton transfer, this work highlights a novel design paradigm for engineering new organic thermochromics with tailored physical properties.

Original languageEnglish
Pages (from-to)1626-1634
Number of pages9
JournalCrystEngComm
Volume21
Issue number10
Early online date7 Feb 2019
DOIs
Publication statusPublished - 14 Mar 2019

Keywords

  • crystal engineering
  • co-crystals
  • thermochromic
  • proton transfer
  • x-ray crystal structure

ASJC Scopus subject areas

  • Chemistry(all)

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