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

Paul Raithby; Joshua Morris; Chris Bowen; Benjamin Coulson; Mark Eaton; Lucy Saunders; Jonathan Skelton; Qingping Wang; Mark R Warren; Yan Zhang; Lauren Hatcher

doi:10.1002/anie.202401552

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

Paul Raithby, Joshua Morris, Chris Bowen, Benjamin Coulson, Mark Eaton, Lucy Saunders, Jonathan Skelton, Qingping Wang, Mark R Warren, Yan Zhang, Lauren Hatcher

Research output: Contribution to journal › Article › peer-review

2 Citations (SciVal)

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 273-100K 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 language	English
Article number	e202401552
Number of pages	11
Journal	Angewandte Chemie International Edition
Volume	63
Issue number	20
Early online date	10 Apr 2024
DOIs	https://doi.org/10.1002/anie.202401552
Publication status	Published - 13 May 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.

Funding

L.E.H. and B.A.C. acknowledge funding from the Royal Society (URF\\R1\\191104). L.E.H also thanks Diamond Light Source for the award of beamtime to conduct the in situ VT and \u2010cell SCXRD experiments (beamtimes CY28436\u20101 and CY31624\u20101). J.J.M. is grateful to Cardiff University for PhD studentship support. PRR is grateful to the EPSRC for funding (EP/K004956/1). J.M.S. is currently supported by a UKRI Future Leaders Fellowship (MR/T043121/1) and previously held a University of Manchester Presidential Fellowship. The majority of the calculations were performed on the UK national ARCHER2 HPC facility, via J.M.S.\u2019s membership of the UK Materials Chemistry Consortium (MCC), which is funded by the EPSRC (EP/R029431 and EP/X035859). C.B. and Q.W. acknowledge support of UKRI Frontier Research Guarantee on \u201C\u2014\u201D, project EP/X023265/1. Y.Z. is grateful for support from the National Natural Science Foundation of China (No. 52302158). The authors thank Michael Zachariadis of the Imaging Facility at the University of Bath (doi.org/10.15125/mx6j\u20103r54), for their technical support and guidance in this work. E Processing of Smart Porous Electro\u2010Ceramic Transducers ProSPECT

Funders	Funder number
UK Research and Innovation	MR/T043121/1, EP/R029431, EP/X035859, EP/X023265/1
UK Research and Innovation
Engineering and Physical Sciences Research Council	EP/K004956/1
Engineering and Physical Sciences Research Council
National Natural Science Foundation of China	52302158
National Natural Science Foundation of China
Royal Society	URF\R1\191104
Royal Society

Keywords

Nitrosyls
Phase transitions
Piezoelectric
Pyroelectric Photocrystallography

ASJC Scopus subject areas

General Chemistry
Catalysis

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10.1002/anie.202401552Licence: CC BY

Cite this

Raithby, P., Morris, J., Bowen, C., Coulson, B., Eaton, M., Saunders, L., Skelton, J., Wang, Q., Warren, M. R., Zhang, Y., & Hatcher, L. (2024). Exploring Pyroelectricity, Thermal and Photochemical Switching in a Hybrid Organic-Inorganic Crystal by In-situ X-ray Diffraction. Angewandte Chemie International Edition, 63(20), Article e202401552. https://doi.org/10.1002/anie.202401552

Raithby, P, Morris, J, Bowen, C, Coulson, B, Eaton, M, Saunders, L, Skelton, J, Wang, Q, Warren, MR, Zhang, Y & Hatcher, L 2024, 'Exploring Pyroelectricity, Thermal and Photochemical Switching in a Hybrid Organic-Inorganic Crystal by In-situ X-ray Diffraction', Angewandte Chemie International Edition, vol. 63, no. 20, e202401552. https://doi.org/10.1002/anie.202401552

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

Abstract

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