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Driving Barocaloric Effects in a Molecular Spin-Crossover Complex at Low Pressures

  • Jinyoung Seo
    Jinyoung Seo
    Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States
    More by Jinyoung Seo
  • Jason D. Braun
    Jason D. Braun
    Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States
  • Vidhya M. Dev
    Vidhya M. Dev
    Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States
  • , and 
  • Jarad A. Mason*
    Jarad A. Mason
    Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States
    *Email: [email protected]
Cite this: J. Am. Chem. Soc. 2022, 144, 14, 6493–6503
Publication Date (Web):March 31, 2022
https://doi.org/10.1021/jacs.2c01315
Copyright © 2022 American Chemical Society
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Abstract

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Barocaloric effects─thermal changes in a material induced by applied hydrostatic pressure─offer promise for creating solid-state refrigerants as alternatives to conventional volatile refrigerants. To enable efficient and scalable barocaloric cooling, materials that undergo high-entropy, reversible phase transitions in the solid state in response to a small change in pressure are needed. Here, we report that pressure-induced spin-crossover (SCO) transitions in the molecular iron(II) complex Fe[HB(tz)3]2 (HB(tz)3 = bis[hydrotris(1,2,4-triazol-1-yl)borate]) drive giant and reversible barocaloric effects at easily accessible pressures. Specifically, high-pressure calorimetry and powder X-ray diffraction studies reveal that pressure shifts as low as 10 bar reversibly induce nonzero isothermal entropy changes, and a pressure shift of 150 bar reversibly induces a large isothermal entropy change (>90 J kg–1 K–1) and adiabatic temperature change (>2 K). Moreover, we demonstrate that the thermodynamics of the SCO transition can be fine-tuned through systematic deuteration of the tris(triazolyl)borate ligand. These results provide new insights into pressure-induced SCO transitions and further establish SCO materials as promising barocaloric materials.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.2c01315.

  • Additional experimental details, high-pressure calorimetry data, entropy curves used to evaluate barocaloric effects, PXRD data, single-crystal XRD data, and summary of all the structural and thermodynamic data (PDF)

Accession Codes

CCDC 21497602149761 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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Cited By

This article is cited by 1 publications.

  1. Damian Paliwoda, Laure Vendier, William Nicolazzi, Gábor Molnár, Azzedine Bousseksou. Pressure Tuning of Coupled Structural and Spin State Transitions in the Molecular Complex [Fe(H2B(pz)2)2(phen)]. Inorganic Chemistry 2022, 61 (40) , 15991-16002. https://doi.org/10.1021/acs.inorgchem.2c02286

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