Exploring Pyroelectricity, Thermal and Photochemical Switching in a Hybrid Organic-Inorganic Crystal by In Situ X-Ray Diffraction

Joshua J Morris; Chris R Bowen; Ben A Coulson; Mark Eaton; Paul R Raithby; Lucy K Saunders; Jonathan M Skelton; Qingping Wang; Mark R Warren; Yan Zhang; Lauren E Hatcher

doi:10.1002/anie.202401552

Exploring Pyroelectricity, Thermal and Photochemical Switching in a Hybrid Organic-Inorganic Crystal by In Situ X-Ray Diffraction

Angew Chem Int Ed Engl. 2024 Mar 18:e202401552. doi: 10.1002/anie.202401552. Online ahead of print.

Authors

Affiliations

¹ School of Chemistry, Cardiff University Main Building, Park Place, Cardiff, CF10 AT, UK.
² Department of Mechanical Engineering, University of Bath, Claverton Down, Bath, BA2 7AY, UK.
³ School of Engineering, Cardiff University Queen's Buildings, The Parade, Cardiff, CF24 3AA, UK.
⁴ Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK.
⁵ Diamond Light Source, Harwell Science and Innovation Campus, Fermi Ave, Didcot, OX11 0DE, UK.
⁶ Department of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
⁷ State Key Laboratory of Powder Metallurgy, Central South University, Changsha, Hunan, 410083, China.

PMID: 38497693
DOI: 10.1002/anie.202401552

Abstract

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 273-100 K induces gradual ordering, while cooling under an applied field (E=+40 kVcm^-1) induces a sudden phase change at 140 K. 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.

Keywords: Nitrosyls; Phase transitions; Piezoelectric; Pyroelectric Photocrystallography.

Abstract

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