The switching behavior of the novel hybrid material (FA)Na[Fe(CN)5(NO)].H2O (1) in response to temperature (T), light irradiation and electric field (E) is studied using in-situ X-ray diffraction (XRD). Crystals of 1 display piezoelectricity, pyroelectricity, second and third harmonic generation. XRD shows that the FA+ are disordered at room-temperature, but stepwise cooling from 273-100K induces gradual ordering, while cooling under an applied field (E = +40kVcm-1) induces a sudden phase change at 140K. Structural-dynamics calculations suggest the field pushes the system into a region of the structural potential-energy surface that is otherwise inaccessible, demonstrating that application of T and E offers an effective route to manipulating the crystal chemistry of these materials. Photocrystallography also reveals photoinduced linkage isomerism, which coexists with but is not correlated to other switching behaviors. These experiments highlight a new approach to in-situ studies of hybrid materials, providing insight into the structure-property relationships that underpin their functionality.
Original languageEnglish
Article numbere202401552
Number of pages11
JournalAngewandte Chemie-International Edition
Early online date10 Apr 2024
Publication statusE-pub ahead of print - 10 Apr 2024

Data Availability Statement

The manuscript is accompanied by detailed Supporting Information available in PDF format, inclusive of computational data and methods. The authors have cited additional references within the Supporting Information. Deposition Numbers 2326867–2326893, 2327111–2327133 and 2339009–2339023 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe via www.ccdc.cam.ac.uk/structures. Further experimental data are available via the Cardiff University Research Portal at https://doi.org/10.17035/d.2024.0313960534 and computational data are available at https://doi.org/10.17632/svtrf2g449.1.


  • Nitrosyls
  • Phase transitions
  • Piezoelectric
  • Pyroelectric Photocrystallography

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis


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